Structurally-colored articles and methods for making and using structurally-colored articles

ABSTRACT

As described above, one or more aspects of the present disclosure provide articles having achromatic structural color, and methods of making articles having achromatic structural color. The present disclosure provides for articles that exhibit achromatic structural colors upon exposure to white light (e.g., sunlight, artificial light, or a combination) through the use of an optical element, where achromatic structural colors are visible colors produced, at least in part, through optical effects (e.g., through scattering, refraction, reflection, interference, and/or diffraction of visible wavelengths of light). The optical element (e.g., a single-layer reflector or single-layer filter or a multilayer reflector or a multilayer filter; inorganic and/or organic material) can include a reflective layer(s) and/or a constituent layer(s).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to, co-pending U.S. Patent Applicationentitled “STRUCTURALLY-COLORED ARTICLES AND METHODS FOR MAKING AND USINGSTRUCTURALLY-COLORED ARTICLES,” filed on Oct. 15, 2019, and assignedapplication No. 62,915,061 which is incorporated herein by reference intheir entireties.

BACKGROUND

Structural color is caused by the physical interaction of light with themicro- or nano-features of a surface and the bulk material as comparedto color derived from the presence of dyes or pigments that absorb orreflect specific wavelengths of light based on the chemical propertiesof the dyes or pigments. Color from dyes and pigments can be problematicin a number of ways. For example, dyes and pigments and their associatedchemistries for fabrication and incorporation into finished goods maynot be environmentally friendly.

BRIEF DESCRIPTION OF THE DRAWINGS

Further embodiments of the present disclosure will be more readilyappreciated upon review of the detailed description of its variousembodiments, described below, when taken in conjunction with theaccompanying drawings.

FIGS. 1A-1M shows various articles of footwear, apparel, athleticequipment, container, electronic equipment, and vision wear that includethe primer layer in accordance with the present disclosure, while FIGS.1N(a)-1Q(e) illustrate additional details regarding different types offootwear.

FIG. 2A illustrates a side view of exemplary optical element of thepresent disclosure.

FIG. 2B illustrates a side view of exemplary optical element of thepresent disclosure.

FIGS. 3A and 3B illustrate graphs of wavelength as a function of percentreflectance and absorbance, respectively, where each graph isillustrative of measurement of various parameters when the achromaticstructural color is black.

FIGS. 4A and 4B illustrate graphs of wavelength as a function of percentreflectance and absorbance, respectively, where each graph isillustrative of measurement of various parameters when the achromaticstructural color is white.

FIGS. 5A and 5B illustrate graphs of wavelength as a function of percentreflectance and absorbance, respectively, where each graph isillustrative of measurement of various parameters when the achromaticstructural color is neutral gray.

The drawings described herein are for illustration purposes only and arenot intended to limit the scope of the present disclosure in any way.

DESCRIPTION

The present disclosure provides for articles that exhibit achromaticstructural colors upon exposure to white light (e.g., sunlight,artificial light, or a combination) through the use of an opticalelement, where achromatic structural colors are visible colors produced,at least in part, through optical effects (e.g., through scattering,refraction, reflection, interference, and/or diffraction of visiblewavelengths of light). The optical element (e.g., a single-layerreflector or single-layer filter or a multilayer reflector or amultilayer filter; inorganic and/or organic material) can include areflective layer(s) and/or a constituent layer(s). In one embodiment,the reflective layer(s) and/or constituent layers can be flat (planar)or substantially flat (substantially planar) or can have a texturedtopography or textured surface. The optical element may absorb allwavelengths within the range of about 380 to 740 nanometers tosubstantially the same degree (e.g., plus or minus about 15 percent orless). The optical element may reflect all wavelengths within the rangeof about 380 to 740 nanometers to substantially the same degree (e.g.,plus or minus about 15 percent or less).

The achromatic color can be selected from black, white, or neutral gray.A “chromatic color” is a color in which one particular wavelength or huepredominates, while an “achromatic color” is a color in which noparticular wavelength or hue predominates, as all wavelengths or huesare present in equal parts or substantially equal parts. When theachromatic color is black, white, or a neutral gray, the phrase “pureachromatic color” can be used. As used herein, the achromatic colorexcludes the following colors: a warm gray, a warm brown, a warm tan, acool gray, a cool brown, a cool tan. For example, a warm gray, a warmbrown, and a warm tan would be colors in which yellow or redpredominates and so would not be achromatic. Similarly, a cool gray, acool brown, and a cool tan would be colors in which blue or greenpredominates, and so would not be achromatic. Achromatic gray caninclude gainsboro gray, light gray, silver gray, medium gray, spanishgray, gray, dim gray, Davy's gray, jet gray, and the middle grays.

When the achromatic structural color is black, the optical elementreflects all or substantially all of the wavelengths within the range ofabout 380 to 740 nanometers to substantially the same degree. Thepercent reflectance of the optical element is about 2 percent or less,about 1 percent or less, about 0.5 percent or less, about 0.1 percent orless, or 0 percent within the range of about 380 to 740 nanometers tosubstantially the same degree when the achromatic structural color isblack. The percent absorbance of the optical element is about 98 percentor more, about 99 percent or more, about 99.5 percent or more, about99.9 percent or more, about 100 percent within the range of about 380 to740 nanometers to substantially the same degree when the achromaticstructural color is black.

When the achromatic structural color is white, the optical elementabsorbs all wavelengths within the range of about 380 to 740 nanometersto substantially the same degree. The percent absorbance of the opticalelement is about 2 percent or less, about 1 percent or less, about 0.5percent or less, about 0.1 percent or less, or 0 percent within therange of about 380 to 740 nanometers to substantially the same degreewhen the achromatic structural color is white. The percent reflectanceof the optical element is about 98 percent or more, about 99 percent ormore, about 99.5 percent or more, about 99.9 percent or more, or about100 percent within the range of about 380 to 740 nanometers tosubstantially the same degree when the achromatic structural color iswhite.

If the achromatic structural color is neutral gray, then the percentabsorbance is between the percent absorbance of black and white or thepercent reflectance is between the percent absorbance of black andwhite. When the achromatic structural color is neutral gray, the percentabsorbance of the optical element is about 2 to 98 percent, about 1 to99 percent, about 0.5 to about 99.5 percent, or about 0.1 to about 99.9,within the range of about 380 to 740 nanometers to substantially thesame degree. The percent reflectance of the optical element is about 2to 98 percent, about 1 to 99 percent, about 0.5 to about 99.5 percent,or about 0.1 to about 99.9, within the range of about 380 to 740nanometers to substantially the same degree, when the achromaticstructural color is neutral gray.

The achromatic structural color imparted by the optical element can beindependent of the angle of incident light upon the optical element oris independent upon observation angle of the optical element.Alternatively, the achromatic structural color of the optical elementcan be dependent of the angle of incident light upon the optical elementor is dependent upon observation angle of the optical element.

The dependence upon the angle of incident light or the observation angleupon the optical element can be evaluated using the CIE 1976 color spaceunder a given illumination condition at two observation angles of about−15 and 180 or about −15 degrees and +60 degrees and which are at least15 degrees apart from each other. Under CIE 1976 color space under agiven illumination condition a color measurement having coordinates L₁*and a₁* and b₁* can be obtained and measurements. A first colormeasurement can have coordinates L₁* and a₁* and b₁*, and a second colormeasurement can have coordinates L₂* and a₂* and b₂*. For example, at afirst observation angle the achromatic structural color is a firstachromatic structural color having coordinates L₁* and a₁* and b₁* andat a second observation angle the structural color is a secondachromatic structural color having coordinates L₂* and a₂* and b₂*. L₁*and L₂* values may be the same or different, a₁* and a₂* coordinatevalues may be the same or different, b₁* and b₂* coordinate values maybe the same or different, and the ΔE*_(ab) between the first colormeasurement and the second color measurement is less than or equal toabout 100, where ΔE*_(ab)=[(L₁*-L₂*)²+(a₁*a₂*)²+(b₁*-b₂*)²]^(1/2). In anaspect, each of a* and b* (a₁*, b₁*, a₂*, and b₂*) have a value of 0 orare very close to 0 for an achromatic structural color. In this regard,the change is primarily in L₁* and L₂*.

A first color measurement at the first observation angle can be obtainedand has coordinates L₁* and a₁* and b₁*, while a second colormeasurement at the second observation angle can be obtained and hascoordinates L₂* and a₂* and b₂* can be obtained (e.g., each a* and b*can have a value of 0 or are very close to 0). In instances where theΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 2.2 or is less than or equalto about 3, the first achromatic structural color associated with thefirst color measurement and the second achromatic structural colorassociated with the second color measurement are the same or notperceptibly different to an average observer. In other words, theachromatic structural color is independent of the angle of incidentlight upon the optical element or is independent of observation angle ofthe optical element. If the ΔE*_(ab) between the first color measurementand the second color measurement is greater than 3 or optionally greaterthan about 4 or 5, then the first achromatic structural color associatedwith the first color measurement and the second achromatic structuralcolor associated with the second color measurement are different orperceptibly different to an average observer. Here, the achromaticstructural color is dependent on the angle of incident light upon theoptical element and/or is dependent on the observation angle of theoptical element.

In an alternative approach, if the percent difference between one ormore of values L₁* and L₂*, a₁* and a₂*, and b₁* and b₂* (e.g., each ofa* and b* can have a value of 0 or are very close to 0) is less than 20percent, less than 10 percent, or less than 5 percent, the firstachromatic structural color associated with the first color measurementand the second achromatic structural color associated with the secondcolor measurement are the same or not perceptibly different to anaverage observer. The achromatic structural color is independent of theangle of incident light upon the optical element or is independent uponobservation angle of the optical element. In situations where thepercent difference between one or more of values L₁* and L₂* a₁* anda₂*, and b₁* and b₂* is greater than 20 percent, the first achromaticstructural color associated with the first color measurement and thesecond achromatic structural color associated with the second colormeasurement are different or perceptibly different to an averageobserver. In this instance the achromatic structural color is dependenton the angle of incident light upon the optical element and/or isdependent on the observation angle of the optical element.

The article includes the optical element including the reflectivelayer(s), constituent layer(s), an optional textured surface, and, wherethe optical element is disposed on the surface of the article with theoptional textured surface between the optical element and the surface orwhere the textured surface is part of the optical element, dependingupon the design. The combination of the optical element and the optionaltextured surface can impart the achromatic structural color, to thearticle, where the achromatic structural color can be designed to bedifferent than the color of the components of the optical element or theunderlying material, optionally with or without the application ofpigments or dyes to the article. In this way, the achromatic structuralcolor imparts an aesthetically appealing achromatic color to the articlewithout requiring the use of inks or pigments and the environmentalimpact associated with their use. In the alternative, the optionaltextured surface does not contribute to imparting the achromaticstructural color to the article so that the optical element (excludingthe textured surface) imparts the achromatic structural color (in otherwords, the achromatic structural color is the same with or without thetextured surface), where the achromatic structural color can be designedto be different than the color of the components of the optical elementor the underlying material, optionally with or without the applicationof pigments or dyes to the article.

The article can be a finished article such as, for example, an articleof footwear, apparel or sporting equipment. The article can be acomponent of an article of footwear, apparel or sporting equipment, suchas, for example, an upper or a sole for an article of footwear, awaistband or arm or hood of an article of apparel, a brim of a hat, aportion of a backpack, or a panel of a soccer ball, and the like. Forexample, the optical element can be disposed (e.g., affixed, attached,adhered, bonded, joined) on a surface of one or more components of thefootwear, such as on the shoe upper and/or the sole. The optical elementcan be incorporated into the sole by incorporating it into a cushioningelement such as a bladder or a foam. The sole and/or upper can bedesigned so that one or more portions of the structurally achromaticallycolored component are visible in the finished article, by including anopening, or a transparent component covering the structurallyachromatically colored component, and the like.

The present disclosure provides for an article comprising: an opticalelement on a surface of the article, wherein the optical element impartsa structural color to the article, wherein the structural color is anachromatic color

The present disclosure provides for a method, comprising: disposing anoptical element on a surface of an article according those describedabove and herein. The present disclosure provides for an articlecomprising: a product of the method according those described above andherein.

The present disclosure will be better understood upon reading thefollowing numbered features, which should not be confused with theclaims. Any of the numbered features below can, in some instances, becombined with features described elsewhere in this disclosure and suchcombinations are intended to form part of the disclosure and thesecombinations can be claimed.

-   Feature 1. An article comprising:

an optical element on a surface of the article, wherein the opticalelement imparts a structural color to the article, wherein thestructural color is an achromatic color, optionally wherein an observerhaving 20/20 visual acuity and normal color vision from a distance ofabout 1 meter from the article considers the structural colorachromatic.

-   Feature 2. The article of feature 1, wherein the optical element    absorbs all wavelengths within the range of about 380 to 740    nanometers to substantially the same degree (optionally wherein    substantially the same degree is plus or minus about 5 percent, plus    or minus about 10 percent, plus or minus about 15 percent) and/or    wherein the optical element reflects all wavelengths within the    range of about 380 to 740 nanometers to substantially the same    degree (optionally wherein substantially the same degree is plus or    minus about 5 percent, plus or minus about 10 percent, plus or minus    about 15 percent).-   Feature 3. The article of feature 1, wherein the optical element, as    disposed onto the article, when measured according to the CIE 1976    color space under a given illumination condition at an observation    angle has a color measurement that corresponds with the structural    color, wherein the color measurement has coordinates L* and a* and    b*, and optionally wherein both of a* and b* are equal to 0 or    optionally wherein when a* or b* or both a* and b* are not equal to    0, where a* and b* are close enough to 0 that to an observer having    20/20 visual acuity and normal color vision from a distance of about    1 meter from the article considers the structural color achromatic.-   Feature 4. The article of any preceding feature, wherein the    achromatic color is selected from black, white, or neutral gray.-   Feature 5. The article of feature 4, wherein the achromatic color is    black.-   Feature 6. The article of feature 5, wherein the optical element    reflects all wavelengths within the range of about 380 to 740    nanometers to substantially the same degree.-   Feature 7. The article of feature 5, wherein the percent reflectance    of the optical element is about 2 percent or less, about 1 percent    or less, about 0.5 percent or less, about 0.1 percent or less, or 0    percent within the range of about 380 to 740 nanometers.-   Feature 8. The article of feature 5, wherein the percent absorbance    of the optical element is about 98 percent or more, about 99 percent    or more, about 99.5 percent or more, about 99.9 percent or more, 100    percent within the range of about 380 to 740 nanometers.-   Feature 9. The article of feature 4, wherein the achromatic color is    white, optionally wherein the optical element absorbs all    wavelengths within the range of about 380 to 740 nanometers to    substantially the same degree.-   Feature 10. The article of feature 9, wherein the percent absorbance    of the optical element is about 2 percent or less, about 1 percent    or less, about 0.5 percent or less, about 0.1 percent or less, 0    percent within the range of about 380 to 740 nanometers.-   Feature 11. The article of feature 4, wherein the achromatic color    is white, wherein the percent reflectance of the optical element is    about 98 percent or more, about 99 percent or more, about 99.5    percent or more, about 99.9 percent or more, 100 percent within the    range of about 380 to 740 nanometers.-   Feature 12. The article of feature 4, wherein the achromatic color    is neutral gray.-   Feature 13. The article of feature 12, wherein the percent    absorbance of the optical element is about 2 to 98, about 1 to 99    percent, about 0.5 to about 99.5 percent, about 0.1 to about 99.9,    within the range of about 380 to 740 nanometers.-   Feature 14. The article of feature 12, wherein the percent    reflectance of the optical element is about 2 to 98, about 1 to 99    percent, about 0.5 to about 99.5 percent, about 0.1 to about 99.9,    within the range of about 380 to 740 nanometers.-   Feature 15. The article of any preceding feature, wherein the    achromatic structural color has no hue or chroma.-   Feature 16. The article of any preceding feature, wherein the    achromatic structural color is independent upon observation angle or    the achromatic structural color is dependent upon observation angle.-   Feature 17. A method, comprising:

disposing an optical element on a surface of an article according to anyone of features 1 to 16.

-   Feature 18. The method of feature 17, wherein disposing the optical    element comprises forming the optical element on the surface of the    article.-   Feature 19. The method of any one of the preceding features, wherein    disposing the optical element comprises forming the optical element    on a surface of a component, and then disposing the component with    the optical element on a surface of the article; optionally wherein    the component is a film, or a textile, or a molded component.-   Feature 20. The method of any one of the preceding features, wherein    forming the optical element comprises using: physical vapor    deposition, electron beam deposition, atomic layer deposition,    molecular beam epitaxy, cathodic arc deposition, pulsed laser    deposition, sputtering, chemical vapor deposition, plasma-enhanced    chemical vapor deposition, low pressure chemical vapor deposition,    wet chemistry techniques, or a combination thereof.-   Feature 21. The method of any one of the preceding features, wherein    disposing the optical element comprises depositing the at least one    reflective layer and the at least two constituent layers of the    optical element using a deposition process, wherein the method    optionally includes depositing a first reflective layer comprising a    metal or metal oxide or stainless steel, depositing a first    constituent layer comprising a metal oxide on the first reflective    layer, and depositing a second constituent layer comprising a metal    oxide on the first reflective layer.-   Feature 22. An article comprising: a product of the method of any    one of the preceding method features.-   Feature 23. The methods and/or articles of any one of the preceding    features, wherein the article comprises a polymer material.-   Feature 24. The methods and/or articles of any one of the preceding    features, wherein the optical element is disposed on the polymer    material.-   Feature 25. The methods and/or articles of any one of the preceding    features, wherein the optical element is a single-layer reflector or    single-layer filter or a multilayer reflector or a multilayer    filter, optionally wherein the multilayer reflector has at least two    constituent layers and/or at least one reflector layer, optionally    wherein the at least two constituent layers adjacent to a base    reflective layer have different refractive indices, optionally    wherein each constituent layer of the multilayer reflector has a    thickness of about one quarter of the wavelength of the wavelength    to be reflected.-   Feature 26. The article and/or method of any one of the preceding    articles, wherein the optical element is an optical element, an    organic optical element, or a mixed /organic optical element.-   Feature 27. The article and/or method of any one of the preceding    articles, wherein the organic optical element has at least one layer    that is made of an organic material, optionally wherein the at least    one layer is made of a non-metal or non-metal oxide material,    optionally, wherein at least one layer is made of a polymeric    material (optionally a synthetic polymeric material), optionally    wherein the at least one layer is made an organic material that does    not include a metal or metal oxide, optionally wherein the at least    one layer is made of a polymeric (optionally a synthetic polymeric    material) that does not include a metal or metal oxide.-   Feature 28. The methods and/or articles of any one of the preceding    features, wherein the at least one reflective layer is made of a    material selected from a metal or a metal oxide or stainless steel.-   Feature 29. The methods and/or articles of any one of the features,    wherein the at least one constituent layer is made of a metal or    metal oxide.-   Feature 30. The methods and/or articles of any one of the preceding    features, wherein adjacent constituent layers have different    refractive indices.-   Feature 31. The methods and/or articles of any one of the preceding    features, wherein each constituent layer of the multilayer reflector    has a thickness of about one quarter of the wavelength of the    wavelength to be reflected.-   Feature 32. The methods and/or articles of any of the preceding    features, wherein the optical element has a thickness of about 100    to about 700 nanometers, or of about 200 to about 500 nanometers.-   Feature 33. The methods and/or articles of any one of the preceding    features, wherein a base reflective layer is made of a material    selected from metal or metal oxide or stainless steel.-   Feature 34. The methods and/or articles of any one of the preceding    features, wherein the metal is selected from the group consisting    of: titanium, aluminum, silver, zirconium, chromium, magnesium,    silicon, gold, platinum, and a combination thereof.-   Feature 35. The methods and/or articles of any one of the preceding    features, the base reflective layer has a thickness of at least 10    nanometers (optionally at least 30 nanometers, optionally at least    40 nanometers, optionally at least 50 nanometers, optionally at    least 60 nanometers, optionally a thickness of from about 10    nanometers to about 100 nanometers, or of from about 30 nanometers    to about 80 nanometers, or from about 40 nanometers to about 60    nanometers).-   Feature 36. The methods and/or articles of any one of the preceding    features, wherein the constituent layer is made of a material    selected from a metal or metal oxide, optionally wherein the    material is selected from the group consisting of: silicon dioxide,    titanium dioxide, zinc sulphide, magnesium fluoride, tantalum    pentoxide, and a combination thereof.-   Feature 37. The methods and/or articles of any one of the preceding    features, wherein the at least one reflective layer comprises a    titanium layer, wherein the first constituent layer comprises a    titanium dioxide layer, or a silicon layer, and wherein the second    constituent layer comprises a titanium dioxide layer or a silicon    dioxide layer.-   Feature 38. The methods and/or articles of any one of the preceding    features, wherein a layer of the optical element further comprises a    textured surface, and the textured surface and the optical element    impart the achromatic structural color or wherein the textured    surface does not contribute to imparting the achromatic structural    color.-   Feature 39. The methods and/or articles of any one of the preceding    features, wherein the surface of the article is a textured surface,    wherein the optical element is on the textured surface, and the    textured surface of the substrate and the optical element impart the    achromatic structural color or wherein the textured surface does not    contribute to imparting the achromatic structural color.-   Feature 40. The methods and/or articles of any one of the preceding    features, wherein the textured surface includes a plurality of    profile features and flat planar areas, wherein the profile features    extend above the flat areas of the textured surface, optionally    wherein the dimensions of the profile features, a shape of the    profile features, a spacing among the plurality of the profile    features, in combination with the optical element create the    achromatic structural color (or optionally the dimensions of the    profile features, a shape of the profile features, a spacing among    the plurality of the profile features do not contribute to the    creation of the achromatic structural color), optionally wherein the    profile features are in random positions relative to one another for    a specific area, optionally wherein the spacing among the profile    features is set to reduce distortion effects of the profile features    from interfering with one another in regard to the achromatic    structural color of the article, optionally wherein the profile    features and the flat areas result in at least one layer of the    optical element having an undulating topography across the textured    surface, wherein there is a planar region between neighboring    profile features that is planar with the flat planar areas of the    textured surface, wherein the planar region has dimensions relative    to the profile features to impart the achromatic structural color,    optionally wherein the profile features and the flat areas result in    each layer of the optical element having an undulating topography    across the textured surface.-   Feature 41. The methods and/or articles of any one of the preceding    features, wherein the article is a fiber.-   Feature 42. The methods and/or methods and/or articles of any one of    the preceding features, wherein the article is a yarn.-   Feature 43. The methods and/or articles of any one of the preceding    features, wherein the article is a monofilament yarn.-   Feature 44. The methods and/or articles of any one of the preceding    features, wherein the article is a textile, optionally a knit    textile, a non-woven textile, a woven textile, a crocheted textile,    or a braided textile.

Feature 45. The methods and/or articles of any one of the precedingfeatures, wherein the article is a knit textile.

-   Feature 46. The methods and/or articles of any one of the preceding    features, wherein the article is a non-woven textile.-   Feature 47. The methods and/or articles of any one of the preceding    features, wherein the article is a non-woven synthetic leather,    optionally wherein the achromatic structural color is visible on a    side of the non-woven synthetic leather intended to be    externally-facing during use.-   Feature 48. The methods and/or articles of any one of the preceding    features, wherein the article is a film.-   Feature 49. The methods and/or articles of any one of the preceding    features, wherein the article is an article of footwear, a component    of footwear, an article of apparel, a component of apparel, an    article of sporting equipment, or a component of sporting equipment.-   Feature 50. The methods and/or articles of any one of the preceding    features, wherein the article is an article of footwear.-   Feature 51. The methods and/or articles of any one of the preceding    features, wherein the article is a sole component of an article of    footwear.-   Feature 52. The methods and/or articles of any one of the preceding    features, wherein the article is an upper component of an article of    footwear.-   Feature 53. The methods and/or articles of any one of the preceding    features, wherein the article is a knit upper component of an    article of footwear.-   Feature 54. The methods and/or articles of any one of the preceding    features, wherein the article is a non-woven synthetic leather upper    for an article of footwear.-   Feature 55. The methods and/or articles of any one of the preceding    features, wherein the article is a bladder including a volume of a    fluid, wherein the bladder has a first bladder wall having a first    bladder wall thickness, wherein the first bladder wall has a gas    transmission rate of 15 cm³/m²·atm·day or less for nitrogen for an    average wall thickness of 20 mils.-   Feature 56. The methods and/or articles of any one of the preceding    features, wherein the article is a bladder, and the optical element    is optionally on an inside surface of the bladder or optionally the    optical element is on an outside surface of the bladder.-   Feature 57. The methods and/or articles of any one of the preceding    features, wherein each of the constituent layers and reflector    layer(s) are three dimensional flat planar surfaces or substantially    three dimensional flat planar surfaces.-   Feature 58. The article and/or method of any of the preceding    features, wherein the profile feature has at least one dimension    greater than 500 micrometers and optionally greater than about 600    micrometers.-   Feature 59. The article and/or method of any of the preceding    features, wherein at least one of the length and width of the    profile feature is greater than 500 micrometers or optionally both    the length and the width of the profile feature is greater than 500    micrometers.-   Feature 60. The article and/or method of any of the preceding    features, wherein the height of the profile features can be greater    than 50 micrometers or optionally greater than about 60 micrometers.-   Feature 61. The article and/or method of any of the preceding    features, wherein at least one of the length and width of the    profile feature is less than 500 micrometers or both the length and    the width of the profile feature is less than 500 micrometers, while    the height is greater than 50 micrometers.-   Feature 62. The article and/or method of any of the preceding    features, wherein at least one of the length and width of the    profile feature is greater than 500 micrometers or both the length    and the width of the profile feature is greater than 500    micrometers, while the height is greater than 50 micrometers.-   Feature 63. The article and/or method of any of the preceding    features, wherein at least one of the dimensions of the profile    feature is in the nanometer range, while at least one other    dimension is in the micrometer range.-   Feature 64. The article and/or method of any of the preceding    features, wherein the nanometer range is about 10 nanometers to    about 1000 nanometers, while the micrometer range is about 5    micrometers to 500 micrometers.-   Feature 65. The article and/or method of any of the preceding    features, wherein at least one of the length and width of the    profile feature is in the nanometer range, while the other of the    length and the width of the profile feature is in the micrometer    range.-   Feature 66. The article and/or method of any of the preceding    features, wherein the height of the profile features is greater than    250 nanometers.-   Feature 67. The article and/or method of any of the preceding    features, wherein at least one of the length and the width of the    profile feature is in the nanometer range and the other in the    micrometer range, where the height is greater than 250 nanometers.-   Feature 68. The article and/or method of any of the preceding    features, wherein spatial orientation of the profile features is    periodic.-   Feature 69. The article and/or method of any of the preceding    features, wherein spatial orientation of the profile features is a    semi-random pattern or a set pattern.-   Feature 70. The article and/or method of any of the preceding    features, wherein the surface of the one or more layers of the    optical element are a substantially three dimensional flat planar    surface or a three dimensional flat planar surface, optionally    wherein the area of the substantially three dimensional flat planar    surface or a three dimensional flat planar surface is about 1    centimeter squared to about 5 centimeter squared, about 1 centimeter    squared to about 10 centimeter squared, about 1 centimeter squared    to about 15 centimeter squared, about 1 centimeter squared to about    20 centimeter squared, about 3 centimeter squared to about 10    centimeter squared, about 5 centimeter squared to about 20    centimeter squared, or about 5 centimeter squared to about 50    centimeter squared.-   Feature 71. The article and/or method of any one of the preceding    features, wherein a layer of the optical element further comprises a    textured surface.-   Feature 72. The article and/or method of feature 71, wherein a layer    of the optical element further comprises a textured surface, wherein    the optical element is on the textured surface, and a lightness    (e.g., L* of CIE 1976 color space or CIELAB) of the achromatic    structural color is altered by the textured surface, as determined    by comparing the optical element comprising the textured surface of    a substantially identical optical element which is free of the    textured surface.-   Feature 73. The article and/or method of feature 71, wherein a layer    of the optical element further comprises a textured surface, wherein    the optical element is on the textured surface, wherein the textured    surface reduces or eliminates shift of the achromatic structural    color as a viewing angle is varied from a first viewing angle to a    second viewing angle, as compared to a substantially identical    optical element which is free of the textured surface.-   Feature 74. The article and/or method of feature 71, wherein a layer    of the optical element further comprises a textured surface, wherein    the optical element is on the textured surface, and a lightness    (e.g., L* of CIE 1976 color space or CIELAB) (optionally a hue    and/or a chroma) is unaffected by or substantially unaffected by the    textured surface, as determined by comparing the optical element    comprising the textured surface to a substantially identical optical    element which is free of the textured surface.-   Feature 75. The article and/or method of feature 71, wherein a layer    of the optical element further comprises a textured surface, wherein    the optical element is on the textured surface, wherein shift of the    achromatic structural color is unaltered by or substantially the    same as a viewing angle is varied from a first viewing angle to a    second viewing angle, as compared to a substantially identical    optical element which is free of the textured surface.-   Feature 76. The article and/or method of any one of the preceding    features, wherein the surface of the article is a textured surface,    wherein the optical element is on the textured surface.-   Feature 77. The article and/or method of feature 76, wherein the    surface of the article is a textured surface, wherein the optical    element is on the textured surface, and a lightness (e.g., L* of CIE    1976 color space or CIELAB), is altered by the textured surface, as    determined by comparing the optical element comprising the textured    surface of a substantially identical optical element on a surface of    a substantially identical article which is free of the textured    surface.-   Feature 78. The article and/or method of feature 76, wherein the    surface of the article is a textured surface, wherein the optical    element is on the textured surface, wherein the textured surface    reduces or eliminates shift of the achromatic structural color as a    viewing angle is varied from a first viewing angle to a second    viewing angle, as compared to a substantially identical optical    element on a surface of a substantially identical article which is    free of the texture.-   Feature 79. The article and/or method of feature 76, wherein the    surface of the article is a textured surface, wherein the optical    element is on the textured surface, and a lightness (e.g., L* of CIE    1976 color space or CIELAB) (optionally a hue and/or a chroma) is    unaffected by or substantially unaffected by the textured surface,    as determined by comparing the optical element comprising the    textured surface to a substantially identical optical element on a    surface of a substantially identical article which is free of the    textured surface.-   Feature 80. The article and/or method of feature 76, wherein the    surface of the article is a textured surface, wherein the optical    element is on the textured surface, wherein shift of the achromatic    structural color is unaltered by or substantially the same as a    viewing angle is varied from a first viewing angle to a second    viewing angle, as compared to a substantially identical optical    element on a surface of a substantially identical article which is    free of the textured surface.-   Feature 81. The article and/or method of any one of the preceding    features, wherein the textured surface includes a plurality of    profile features and flat planar areas, wherein the profile features    extend above the flat areas of the textured surface.-   Feature 82. The article and/or method feature 81, wherein dimensions    of the profile features, a shape of the profile features, a spacing    among the plurality of the profile features, or any combination    thereof, in combination with the optical element, affect a lightness    (e.g., L* of CIE 1976 color space or CIELAB), a shift of the    achromatic structural color as a viewing angle is varied from a    first viewing angle to a second viewing angle, or any combination    thereof.-   Feature 83. The article and/or method of feature 81, wherein a    lightness (e.g., L* of CIE 1976 color space or CIELAB) (optionally a    hue and/or a chroma), a shift of the structural color as a viewing    angle is varied from a first viewing angle to a second viewing    angle, or any combination thereof, are unaffected or substantially    unaffected by dimensions of the profile features, a shape of the    profile features, a spacing among the plurality of the profile    features, or any combination thereof, of the textured surface.-   Feature 84. The article and/or method of feature 81, wherein the    profile features of the textured surface are in random positions    relative to one another within a specific area.-   Feature 85. The article and/or method of feature 81, wherein spacing    among the profile features is random within a specific area.-   Feature 86. The article and/or method of feature 81, wherein spacing    between the profile features, in combination with the optical    element, affects a lightness (e.g., L* of CIE 1976 color space or    CIELAB), a shift of the achromatic structural color as a viewing    angle is varied from a first viewing angle to a second viewing    angle, or any combination thereof.-   Feature 87. The article and/or method of feature 81, wherein a    lightness (e.g., L* of CIE 1976 color space or CIELAB) (optionally a    hue and/or a chroma), a shift of the achromatic structural color as    a viewing angle is varied from a first viewing angle to a second    viewing angle, or any combination thereof, is unaffected by, or    substantially unaffected by, spacing between the profile features in    combination with the optical element.-   Feature 88. The article and/or method of feature 81, wherein the    profile features and the flat areas result in at least one layer of    the optical element having an undulating topography across the    textured surface, and wherein there is a planar region between    neighboring profile features that is planar with the flat planar    areas of the textured surface.-   Feature 89. The article and/or method of feature 88, wherein    dimensions of the planar region relative to the profile features    affect a lightness (e.g., L* of CIE 1976 color space or CIELAB), a    shift of the achromatic structural color as a viewing angle is    varied from a first viewing angle to a second viewing angle, or any    combination thereof.-   Feature 90. The article and/or method of feature 88, wherein a    lightness (e.g., L* of CIE 1976 color space or CIELAB) (optionally a    hue and/or a chroma), a shift of the achromatic structural color as    a viewing angle is varied from a first viewing angle to a second    viewing angle, or any combination thereof, is unaffected by or    substantially unaffected by dimensions of the planar region relative    to the profile features.-   Feature 91. The article and/or method of any one of the preceding    features, wherein the profile features and the flat areas result in    each layer of the optical element having an undulating topography    across the textured surface.-   Feature 92. The article and/or method of feature 91, wherein the    undulating topography of the optical element affects a lightness    (e.g., L* of CIE 1976 color space or CIELAB), a shift of the    achromatic structural color as a viewing angle is varied from a    first viewing angle to a second viewing angle, or any combination    thereof.-   Feature 93. The article and/or method of feature 91, wherein a    lightness (e.g., L* of CIE 1976 color space or CIELAB) (optionally a    hue and/or a chroma), a shift of the achromatic structural color as    a viewing angle is varied from a first viewing angle to a second    viewing angle, or any combination thereof, is unaffected by or    substantially unaffected by the undulating topography of the optical    element.

Now having described embodiments and features and combinations offeatures of the present disclosure generally, additional discussionregarding embodiments features and combinations of features will bedescribed in greater details.

This disclosure is not limited to particular embodiments, features, orcombinations of features described, and as such may, of course, vary.The terminology used herein serves the purpose of describing particularembodiments, features, or combinations of features only, and is notintended to be limiting, since the scope of the present disclosure willbe limited only by the appended claims.

Where a range of values is provided, each intervening value, to thetenth of the unit of the lower limit unless the context clearly dictatesotherwise, between the upper and lower limit of that range and any otherstated or intervening value in that stated range, is encompassed withinthe disclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges and are also encompassedwithin the disclosure, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded in the disclosure.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentdisclosure. Any recited method may be carried out in the order of eventsrecited or in any other order that is logically possible.

Embodiments of the present disclosure will employ, unless otherwiseindicated, techniques of material science, chemistry, textiles, polymerchemistry, and the like, which are within the skill of the art. Suchtechniques are explained fully in the literature.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art of material science, chemistry, textiles, polymer chemistry, andthe like. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentdisclosure, suitable methods and materials are described herein.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” may include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a support”includes a plurality of supports. In this specification and in theclaims that follow, reference will be made to a number of terms thatshall be defined to have the following meanings unless a contraryintention is apparent.

The present disclosure provides for articles that exhibit structuralcolor, specifically achromatic structural color. The achromaticstructural color can be imparted by the optical element having one ormore layers (e.g., reflective layer(s) and/or constituent layer(s)),incorporated onto one or more components of the article, for example,when the article is an article of footwear, on an upper or sole of anarticle of footwear. In one or more embodiments of the presentdisclosure the surface of the article includes the optical element(e.g., a signal-layer reflector, a single-layer filter, a multilayerreflector or a multilayer filter), where at least one layer is flat (orplanar) or substantially flat (or substantially planar), and where theoptical element imparts achromatic structural color. In one or moreadditional embodiments of the present disclosure the surface of thearticle includes the optical element (e.g., a signal-layer reflector, asingle-layer filter, a multilayer reflector or a multilayer filter), andis optionally a textured surface or the layers have a texturedtopography, where the optical element and optionally the texturedsurface or textured topography impart achromatic structural color or thetextured surface or textured topography do not contribute to impartingthe achromatic structural color. The optional textured surface can bedisposed between the optical element and the surface or be part of theoptical element, depending upon the design. The optical element can bedisposed on or is an integral part of a surface of the article.

An “achromatic color” is a color in which no particular wavelength orhue predominates, as all wavelengths or hues are present in equal partsor substantially equal parts. The achromatic color can have no hue orchroma. The achromatic color can be selected from black, white, orneutral gray. The wavelength range can be about 380 to 740 nanometersand can be measured as a function of absorbance or reflectance, each ofwhich can be used to define the achromatic structural color imparted bythe optical element. FIGS. 3A and 3B illustrate graphs of wavelength asa function of percent reflectance and absorbance, respectively, whereeach graph is illustrative of measurement of various parameters wherethe achromatic structural color is black. Similarly, FIGS. 4A and 4B and5A and 5B illustrate graphs of wavelength as a function of percentreflectance and absorbance, respectively, where each graph isillustrative of measurement of various parameters for white and neutralgray (e.g., three curves (a)-(c) illustrate possible neutral grays),respectively.

In regard to absorbance, the optical element absorbs all wavelengthswithin the range of about 380 to 740 nanometers to substantially thesame degree, where the percent absorbance correlates to the particularachromatic structural color. “Substantially the same degree” as usedherein for absorbance and reflectance encompasses plus or minus about 5percent, plus or minus about 10 percent, plus or minus about 15 percent.The percent absorbance of the optical element is about 98 percent ormore (e.g., about 98 to 100 percent), about 99 percent or more (e.g.,about 99 to 100 percent), about 99.5 percent or more (e.g., about 99.5to 100 percent), about 99.9 percent or more (e.g., about 99.9 to 100percent), about 100 percent within the range of about 380 to 740nanometers to substantially the same degree when the achromaticstructural color is black. The percent absorbance of the optical elementis about 2 percent or less (e.g., 0 to about 2 percent), about 1 percentor less (e.g., 0 to about 1 percent), about 0.5 percent or less (e.g.,about 0 to 0.5 percent), about 0.1 percent or less (e.g., about 0 to 0.1percent), or about 0 percent within the range of about 380 to 740nanometers to substantially the same degree when the achromaticstructural color is white. When the achromatic structural color isneutral gray, the percent absorbance of the optical element is about 2to 98, about 1 to 99 percent, about 0.5 to about 99.5 percent, about 0.1to about 99.9, within the range of about 380 to 740 nanometers tosubstantially the same degree.

In regard to reflectance, the optical element reflects all wavelengthswithin the range of about 380 to 740 nanometers to substantially thesame degree, where the percent absorbance correlates to the particularachromatic structural color. The percent reflectance of the opticalelement is about 2 percent or less (e.g., 0 to about 2 percent), about 1percent or less (e.g., 0 to about 1 percent), about 0.5 percent or less(e.g., about 0 to 0.5 percent), about 0.1 percent or less (e.g., about 0to 0.1 percent), or about 0 percent within the range of about 380 to 740nanometers to substantially the same degree when the achromaticstructural color is black. The percent reflectance of the opticalelement is about 98 percent or more (e.g., about 98 to 100 percent),about 99 percent or more (e.g., about 99 to 100 percent), about 99.5percent or more (e.g., about 99.5 to 100 percent), about 99.9 percent ormore (e.g., about 99.9 to 100 percent), about 100 percent within therange of about 380 to 740 nanometers to substantially the same degreewhen the achromatic structural color is white. The percent reflectanceof the optical element is about 2 to 98, about 1 to 99 percent, about0.5 to about 99.5 percent, about 0.1 to about 99.9, within the range ofabout 380 to 740 nanometers to substantially the same degree, when theachromatic structural color is neutral gray.

The optical element, as disposed onto the article, when measuredaccording to CIE 1976 color space under a given illumination conditionat an observation angle has a color measurement that corresponds withthe achromatic structural color. For example, the first colormeasurement can have coordinates L* and a* and b*, wherein both of a*and b* are equal to 0 or close to 0 (e.g., 0.5 or less, 0.2 or less, 0.1or less or 0.05 or less). In another example, the first colormeasurement can have coordinates L* and a* and b*, wherein a* or b* areequal to about 0 or close to 0 (e.g., 0.5 or less, 0.2 or less, 0.1 orless or 0.05 or less). In this instance, optionally, a* or b* or both ofa* and b* are less than 0.5. 0.2, 0.1, or 0.05, and are within about 10percent of each other. In another example, the color may appear to beachromatic to an observer having 20/20 visual acuity and normal colorvision from a distance of about 1 meter from the article when a* or b*or both a* and b* are 0 or about 0 (e.g., 0.5 or less, 0.2 or less, 0.1or less or 0.05 or less). In another example, the color may appear to beachromatic to an observer having 20/20 visual acuity and normal colorvision from a distance of about 1 meter from the article when a* or b*or both a* and b* are 0 or about 0, where a* or b* or both of a* and b*are less than 0.5. 0.2, 0.1, or 0.05, and are within about 10 percent ofeach other.

The optical element can have an achromatic structural color that can beindependent of the angle of incident light upon the optical element. Inaddition, the optical element can have an achromatic structural colorthat is independent of the observation angle.

The optical element can impart an achromatic structural color that canbe dependent of the angle of incident light upon the optical element,where the achromatic color is different at two, three, or more differentangles (e.g., each angle being about 15 degrees, about 20 degrees, about30 degrees, about 45 degrees, about 90 degrees, or more apart) ofincident light (e.g., the shift can be white to black, white to neutralgray to black, two or more different variations of achromatic neutralgray, two or more different shades of white, two or more differentshades of black). In addition, the optical element can have anachromatic structural color that is dependent of the observation angle(e.g., each angle being about 15 degrees, about 20 degrees, about 30degrees, about 45 degrees, about 90 degrees, or more apart), where theachromatic color is different at two, three, or more differentobservation angles (e.g., white to black, white to neutral gray toblack, two or more different variations of achromatic neutral gray, twoor more different shades of white, two or more different shades ofblack). In each instance, the shift can be abrupt (e.g., shift occursover a 1 to 5 degree or 1 to 3 degree, or 1 to 2 degree angle change inobservation or incident light) or can be gradual (e.g., shift over a 5to 10 degree or 5 to 15 degree angle change in observation or incidentlight).

The achromatic structural color imparted by the optical element can bedependent of the angle of incident light upon the optical element ordependent on the observation angle. The dependence upon the angle ofincident light or the observation angle can be evaluated using CIE 1976color space under a given illumination condition at two observationangles (e.g., between −15 degrees and 180 degrees or between −15 degreesand +60 degrees) and which are at least 15 degrees apart from eachother. For example, at a first observation angle the achromaticstructural color is a first achromatic structural color and at a secondobservation angle the achromatic structural color is a second achromaticstructural color. A first color measurement at the first observationangle can be obtained and has coordinates L₁* and a₁* and b₁*, while asecond color measurement at the second observation angle can be obtainedand has coordinates L₂* and a₂* and b₂* can be obtained (e.g., a₁*, b₁*,a₂*, and b₂* can be 0 or close to 0). ΔE*_(ab) can be determined usingthe following equation: ΔE*_(ab)=[(L₁*-L₂*)²+(a₁*a₂*)²+(b₁*b₂*)²]^(1/2).

When ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 2.2 or is less than or equalto about 3, the first achromatic structural color associated with thefirst color measurement and the second achromatic structural colorassociated with the second color measurement are the same or notperceptibly different to an average observer (e.g., the achromaticstructural color is independent of the angle of incident light and/or isindependent of the observation angle). When ΔE*_(ab) between the firstcolor measurement and the second color measurement is greater than 3 oroptionally greater than about 4 or 5, the first achromatic structuralcolor associated with the first color measurement and the secondachromatic structural color associated with the second color measurementare different or perceptibly different to an average observer (e.g., theachromatic structural color is dependent on the angle of incident lightand/or is dependent on observation angle).

In another approach, when the percent difference between one or more ofvalues L₁* and L₂* a₁* and a₂*, and b₁* and b₂* is less than 20 percent,the first achromatic structural color associated with the first colormeasurement and the second achromatic structural color associated withthe second color measurement are the same or not perceptibly differentto an average observer (e.g., the achromatic structural color isindependent of the angle of incident light upon the optical elementand/or is independent upon observation angle of the optical element).When the percent difference between one or more of values L₁* and L₂*a₁* and a₂*, and b₁* and b₂* is greater than 20 percent, the firstachromatic structural color associated with the first color measurementand the second achromatic structural color associated with the secondcolor measurement are different or perceptibly different to an averageobserver (e.g., the achromatic structural color is dependent of theangle of incident light on the optical element and/or is dependent onthe observation angle of the optical element).

As described herein, the optical element is used to impart theachromatic structural color, where the optical element can include oneor a plurality of layers. In an example, the layer(s) can include one ormore reflective layers and/or one or more constituent layers to producethe achromatic structural color. The layers can be flat (or threedimensional flat planar surface) or substantially flat (or substantiallythree dimensional flat planar surface) or can have a texturedtopography. One of the reflective layers can be a base reflective layerdisposed on one side of the optical element; in other words the layerstructure is as follows: base reflective layer/1^(st) constituentlayer/n^(th) constituent layer. Optionally, one of the reflective layerscan be a non-base reflective layer disposed between a pair ofconstituent layers of the optical element; in other words the layerstructure is as follows: base reflective layer/1^(st) constituentlayer/n^(th) constituent layer/non-base reflective layer/m^(th)constituent layer. Also as described herein, the optical element canalso include the optional textured surface, such as a texture layerand/or a textured structure as opposed to a three dimensional flatplanar surface. Additionally and optionally, the optical element caninclude one or more layers (e.g., protection layer, top layer, and thelike). In an embodiment, the reflective layer(s) can be omitted and theoptical element only includes constituent layers and can still producethe achromatic structural color, with or without the textured surface.

The base reflective layer can have a percent reflectance of about 50percent or more, about 75 percent or more, about 80 percent or more,about 85 percent or more, about 90 percent or more, or about 95 percentor more. The base reflective layer can have a thickness of at least 10nanometers, optionally at least 30 nanometers, at least 40 nanometers,at least 50 nanometers, at least 60 nanometers, at least 100 nanometers,at least 150 nanometers, optionally a thickness of from about 10nanometers to about 250 nanometers or more, about 10 nanometers to about100 nanometers, about 10 nanometers to about 150 nanometers, about 10nanometers to about 100 nanometers, or of from about 30 nanometers toabout 80 nanometers, or from about 40 nanometers to about 60 nanometers.For example, the base layer can be about 30 to 150 nanometers thick.

The optical element can include one or more non-base reflective layers.The non-base reflective layer can have a minimum percent transmittanceof at least 5 percent, optionally at least 10 percent, at least 15percent, at least 20 percent, at least 30 percent, at least 40 percent,or at least 50 percent, or at least 60 percent. Typically, the basereflective layer has a greater percent reflectance than the non-basereflective layer. The non-base reflective layer can have a thickness ofless than 40 nanometers, optionally less than 30 nanometers, optionallyless than 20 nanometers, optionally less than 10 nanometers. Forexample, the non-base layer can be 20 to 30 nanometers thick. Thenon-base layer is not opaque.

A minimum percent transmittance of greater than 50 percent is an opaquelayer, a minimum percent transmittance of 20 to 50 percent to besemi-transparent, and a minimum percent transmittance of less than 20percent is transparent.

The reflective layer (e.g., base or non-base reflective layer) caninclude a metal layer or an oxide layer, an alloy layer, an organiclayer, or stainless steel, as well as mixtures thereof. The oxide layercan be a metal oxide, a doped metal oxide, or a combination thereof. Themetal layer, the metal oxide or the doped metal oxide can include thefollowing: the transition metals, the metalloids, the lanthanides, andthe actinides, as well as nitrides, oxynitrides, sulfides, sulfates,selenides, tellurides and a combination of these. The metal layer can betitanium, aluminum, silver, zirconium, chromium, magnesium, silicon,gold, platinum, nobium, and a combination thereof. The metal oxide caninclude titanium oxide, silver oxide, aluminum oxide, silicon dioxide,tin dioxide, chromia, iron oxide, nickel oxide, silver oxide, cobaltoxide, zinc oxide, platinum oxide, palladium oxide, vanadium oxide,molybdenum oxide, lead oxide, nobium oxide, and combinations thereof aswell as doped versions of each. In some aspects, the reflective layercan consist essentially of a metal oxide. In some aspects, thereflective layer can consist essentially of titanium dioxide. The metaloxide can be doped with water, inert gasses (e.g., argon), reactivegasses (e.g., oxygen or nitrogen), metals, small molecules, and acombination thereof. In some aspects, the reflective layer can consistessentially of a doped metal oxide or a doped metal oxynitride or both.

The reflective layer can be a coating on the surface of the article. Thecoating can be chemically bonded (e.g., covalently bonded, ionicallybonded, hydrogen bonded, and the like) to the surface of the article.The coating has been found to bond well to a surface made of a polymericmaterial. In an example, the surface of the article can be made of apolymeric material such as a polyurethane, including a thermoplasticpolyurethane (TPU), as those described herein. Additional details aboutthe optical element and the reflective layer(s) are provided herein.

In an embodiment, the imparted achromatic structural color is not usedin combination with a pigment and/or dye. In another aspect, theimparted achromatic structural color is used in combination with apigment and/or dye.

The article including the optical element can be an article ofmanufacture or a component of the article. The article of manufacturecan include footwear, apparel (e.g., shirts, jerseys, pants, shorts,gloves, glasses, socks, hats, caps, jackets, undergarments), containers(e.g., backpacks, bags), and upholstery for furniture (e.g., chairs,couches, car seats), bed coverings (e.g., sheets, blankets), tablecoverings, towels, flags, tents, sails, and parachutes, or components ofany one of these. In addition, the optical element can be used with ordisposed on textiles or other items such as striking devices (e.g.,bats, rackets, sticks, mallets, golf clubs, paddles, etc.), athleticequipment (e.g., golf bags, baseball and football gloves, soccer ballrestriction structures), protective equipment (e.g., pads, helmets,guards, visors, masks, goggles, etc.), locomotive equipment (e.g.,bicycles, motorcycles, skateboards, cars, trucks, boats, surfboards,skis, snowboards, etc.), balls or pucks for use in various sports,fishing or hunting equipment, furniture, electronic equipment,construction materials, eyewear, timepieces, jewelry, and the like.

The article can be an article of footwear. The article of footwear canbe designed for a variety of uses, such as sporting, athletic, military,work-related, recreational, or casual use. Primarily, the article offootwear is intended for outdoor use on unpaved surfaces (in part or inwhole), such as on a ground surface including one or more of grass,turf, gravel, sand, dirt, clay, mud, pavement, and the like, whether asan athletic performance surface or as a general outdoor surface.However, the article of footwear may also be desirable for indoorapplications, such as indoor sports including dirt playing surfaces forexample (e.g., indoor baseball fields with dirt infields).

In particular, the article of footwear can be designed for use in indooror outdoor sporting activities, such as global football/soccer, golf,American football, rugby, baseball, running, track and field, cycling(e.g., road cycling and mountain biking), and the like. The article offootwear can optionally include traction elements (e.g., lugs, cleats,studs, and spikes as well as tread patterns) to provide traction on softand slippery surfaces, where components of the present disclosure can beused or applied between or among the traction elements and optionally onthe sides of the traction elements but on the surface of the tractionelement that contacts the ground or surface. Cleats, studs and spikesare commonly included in footwear designed for use in sports such asglobal football/soccer, golf, American football, rugby, baseball, andthe like, which are frequently played on unpaved surfaces. Lugs and/orexaggerated tread patterns are commonly included in footwear includingboots design for use under rugged outdoor conditions, such as trailrunning, hiking, and military use.

In particular, the article can be an article of apparel (i.e., agarment). The article of apparel can be an article of apparel designedfor athletic or leisure activities. The article of apparel can be aarticle of apparel designed to provide protection from the elements(e.g., wind and/or rain), or from impacts.

In particular, the article can be an article of sporting equipment. Thearticle of sporting equipment can be designed for use in indoor oroutdoor sporting activities, such as global football/soccer, golf,American football, rugby, baseball, running, track and field, cycling(e.g., road cycling and mountain biking), and the like.

FIGS. 1A-1M illustrates footwear, apparel, athletic equipment,container, electronic equipment, and vision wear that include thestructure (e.g., the optical element) of the present disclosure. Astructure including the optical element is represented by hashed areas12A′/12M′-12A″/12M′. The location of the structure is provided only toindicate one possible area that the structure can be located. Also, twolocations are illustrated in some of the figures and one location isillustrated in other figures, but this is done only for illustrationpurposes as the items can include one or a plurality of structure, wherethe size and location can be determined based on the item. Thestructure(s) located on each item can represent a number, letter,symbol, design, emblem, graphic mark, icon, logo, or the like.

FIGS. 1N(a) and 1N(b) illustrate a perspective view and a side view ofan article of footwear 100 that include a sole structure 104 and anupper 102. The structure including the optical element is represented by122 a and 122 b. The sole structure 104 is secured to the upper 102 andextends between the foot and the ground when the article of footwear 100is worn. The primary elements of the sole structure 104 are a midsole114 and an outsole 112. The midsole 114 is secured to a lower area ofthe upper 102 and may be formed of a polymer foam or another appropriatematerial. In other configurations, the midsole 114 can incorporatefluid-filled chambers, plates, moderators, and/or other elements thatfurther attenuate forces, enhance stability, or influence motions of thefoot. The outsole 112 is secured to a lower surface of the midsole 114and may be formed from a wear-resistant rubber material that is texturedto impart traction, for example. The upper 102 can be formed fromvarious elements (e.g., lace, tongue, collar) that combine to provide astructure for securely and comfortably receiving a foot. Although theconfiguration of the upper 102 may vary significantly, the variouselements generally define a void within the upper 102 for receiving andsecuring the foot relative to sole structure 104. Surfaces of the voidwithin upper 102 are shaped to accommodate the foot and can extend overthe instep and toe areas of the foot, along the medial and lateral sidesof the foot, under the foot, and around the heel area of the foot. Theupper 102 can be made of one or more materials such as textiles, apolymer foam, leather, synthetic leather, and the like that are stitchedor bonded together. Although this configuration for the sole structure104 and the upper 102 provides an example of a sole structure that maybe used in connection with an upper, a variety of other conventional ornonconventional configurations for the sole structure 104 and/or theupper 102 can also be utilized. Accordingly, the configuration andfeatures of the sole structure 104 and/or the upper 102 can varyconsiderably.

FIGS. 1O(a) and 1O(b) illustrate a perspective view and a side view ofan article of footwear 130 that include a sole structure 134 and anupper 132. The structure including the optical element is represented by136 a and 136 b/136 b′. The sole structure 134 is secured to the upper132 and extends between the foot and the ground when the article offootwear 130 is worn. The upper 132 can be formed from various elements(e.g., lace, tongue, collar) that combine to provide a structure forsecurely and comfortably receiving a foot. Although the configuration ofthe upper 132 may vary significantly, the various elements generallydefine a void within the upper 132 for receiving and securing the footrelative to the sole structure 134. Surfaces of the void within theupper 132 are shaped to accommodate the foot and can extend over theinstep and toe areas of the foot, along the medial and lateral sides ofthe foot, under the foot, and around the heel area of the foot. Theupper 132 can be made of one or more materials such as textilesincluding natural and synthetic leathers, molded polymeric components,polymer foam, and the like that are stitched or bonded together.

The primary elements of the sole structure 134 are a forefoot component142, a heel component 144, and an outsole 146. Each of the forefootcomponent 142 and the heel component 144 are directly or indirectlysecured to a lower area of the upper 132 and formed from a polymermaterial that encloses a fluid, which may be a gas, liquid, or gel.During walking and running, for example, the forefoot component 142 andthe heel component 144 compress between the foot and the ground, therebyattenuating ground reaction forces. That is, the forefoot component 142and the heel component 144 are inflated and may be pressurized with thefluid to cushion the foot. The outsole 146 is secured to lower areas ofthe forefoot component 142 and the heel component 144 and may be formedfrom a wear-resistant rubber material that is textured to imparttraction. The forefoot component 142 can be made of one or more polymers(e.g., layers of one or more polymers films) that form a plurality ofchambers that includes a fluid such as a gas. The plurality of chamberscan be independent or fluidically interconnected. Similarly, the heelcomponent 144 can be made of one or more polymers (e.g., layers of oneor more polymers films) that form a plurality of chambers that includesa fluid such as a gas and can also be independent or fluidicallyinterconnected. In some configurations, the sole structure 134 mayinclude a foam layer, for example, that extends between the upper 132and one or both of the forefoot component 142 and the heel component144, or a foam element may be located within indentations in the lowerareas of the forefoot component 142 and the heel component 144. In otherconfigurations, the sole structure 132 may incorporate plates,moderators, lasting elements, or motion control members that furtherattenuate forces, enhance stability, or influence the motions of thefoot, for example. Although the depicted configuration for the solestructure 134 and the upper 132 provides an example of a sole structurethat may be used in connection with an upper, a variety of otherconventional or nonconventional configurations for the sole structure134 and/or the upper 132 can also be utilized. Accordingly, theconfiguration and features of the sole structure 134 and/or the upper132 can vary considerably.

FIG. 1O(c) is a cross-sectional view of A-A that depicts the upper 132and the heel component 144. The optical element 136 b can be disposed onthe outside wall of the heel component 144 or alternatively oroptionally the optical element 136 b′ can be disposed on the inside wallof the heel component 144.

FIGS. 1P(a) and 1P(b) illustrate a perspective view and a side view ofan article of footwear 160 that includes traction elements 168. Thestructure including the optical element is represented by 172 a and 172b. The article of footwear 160 includes an upper 162 and a solestructure 164, where the upper 162 is secured to the sole structure 164.The sole structure 164 can include one or more of a toe plate 166 a, amid-plate 166 b, and a heel plate 166 c. The plate can include one ormore traction elements 168, or the traction elements can be applieddirectly to a ground-facing surface of the article of footwear. As shownin FIGS. 1P(a) and (b), the traction elements 168 are cleats, but thetraction elements can include lugs, cleats, studs, and spikes as well astread patterns to provide traction on soft and slippery surfaces. Ingeneral, the cleats, studs and spikes are commonly included in footweardesigned for use in sports such as global football/soccer, golf,American football, rugby, baseball, and the like, while lugs and/orexaggerated tread patterns are commonly included in footwear (not shown)including boots design for use under rugged outdoor conditions, such astrail running, hiking, and military use. The sole structure 164 issecured to the upper 162 and extends between the foot and the groundwhen the article of footwear 160 is worn. The upper 162 can be formedfrom various elements (e.g., lace, tongue, collar) that combine toprovide a structure for securely and comfortably receiving a foot.Although the configuration of the upper 162 may vary significantly, thevarious elements generally define a void within the upper 162 forreceiving and securing the foot relative to the sole structure 164.Surfaces of the void within upper 162 are shaped to accommodate the footand extend over the instep and toe areas of the foot, along the medialand lateral sides of the foot, under the foot, and around the he& areaof the foot. The upper 162 can be made of one or more materials such astextiles including natural and synthetic leathers, molded polymericcomponents, a polymer foam, and the like that are stitched or bondedtogether. In other aspects not depicted, the sole structure 164 mayincorporate foam, one or more fluid-filled chambers, plates, moderators,or other elements that further attenuate forces, enhance stability, orinfluence the motions of the foot. Although the depicted configurationfor the sole structure 164 and the upper 162 provides an example of asole structure that may be used in connection with an upper, a varietyof other conventional or nonconventional configurations for the solestructure 164 and/or the upper 162 can also be utilized. Accordingly,the configuration and features of the sole structure 164 and/or theupper 162 can vary considerably.

FIGS. 1Q(a)-1Q(j) illustrate additional views of exemplary articles ofathletic footwear including various configurations of upper 176. FIG.1Q(a) is an exploded perspective view of an exemplary article ofathletic footwear showing insole 174, upper 176, optional midsole oroptional lasting board 177, and outsole 178, which can take the form ofa plate. Structures including optical elements are represented by 175a-175 d. FIG. 1Q(b) is a top view of an exemplary article of athleticfootwear indicating an opening 183 configured to receive a wearer's footas well as an ankle collar 181 which may include optical element 182.The ankle collar is configured to be positioned around a wearer's ankleduring wear, and optionally can include a cushioning element. Alsoillustrated are the lateral side 180 and medial side 179 of theexemplary article of athletic footwear, FIG. 1Q(c) is a back view of thearticle of footwear depicted in FIG. 1Q(b), showing an optional heelclip 184 that can include optical element 185. FIG. 1Q(d) shows a sideview of an exemplary article of athletic footwear, which may optionallyalso include a tongue 186, laces 188, a toe cap 189, a heel counter 190,a decorative element such as a logo 191, and/or eyestays for the laces192 as well as a toe area 193 a, a heel area 193 b, and a vamp 193 c. Insome aspects, the heel counter 190 can be covered by a layer of knitted,woven, or nonwoven fabric, natural or synthetic leather, film, or othershoe upper material. In some aspects, the eyestays 192 are formed as onecontinuous piece; however, they can also comprise several separatepieces or cables individually surrounding a single eyelet or a pluralityof eyelets. Structures including optical elements are represented by 187a-187 e. While not depicted, optical elements can be present on theeyestays 192 and/or the laces 188. In some configurations, the solestructure can include a sole structure, such as a midsole having acushioning element in part or substantially all of the midsole, and theoptical element can be disposed on an externally-facing side of the solestructure, including on an externally-facing side of the midsole. FIG.1Q(e) is a side view of another exemplary article of athletic footwear.In certain aspects, the upper can comprise one or more containmentelements 194 such as wires, cables or molded polymeric componentextending from the lace structure over portions of the medial andlateral sides of the exemplary article of athletic footwear to the topof the sole structure to provide lockdown of the foot to the solestructure, where the containment element(s) can have an optical element(not shown) disposed on an externally-facing side thereon. In someconfigurations, a rand (not shown) can be present across part or all ofthe biteline 195.

Now having described embodiments of the present disclosure generally,additional details are provided. As has been described herein, theachromatic structural color can include one of black, white, or neutralgray. The achromatic “color” of an article as perceived by a viewer candiffer from the actual achromatic color of the article, as theachromatic color perceived by a viewer is determined by the actualachromatic color of the article (e.g., the achromatic color of the lightleaving the surface of the article), by the presence of optical elementswhich may absorb, refract, interfere with, or otherwise alter lightreflected by the article, the viewer's visual acuity, by the viewer'sability to detect the wavelengths of light reflected by the article, bythe characteristics of the perceiving eye and brain, by the intensityand type of light used to illuminate the article (e.g., sunlight,incandescent light, fluorescent light, and the like), as well as otherfactors such as the coloration of the environment of the article. As aresult, the achromatic color of an object as perceived by a viewer candiffer from the actual achromatic color of the article.

Conventionally, color is imparted to man-made objects by applyingcolored pigments or dyes to the object. Non-structurally coloredmaterials are made of molecules which absorb all but particularwavelengths of light and reflect back the unabsorbed wavelengths, orwhich absorb and emit particular wavelengths of light. In non-structuralcolor, it is the unabsorbed and/or the emitted wavelengths of lightwhich impart the color to the article. As the color-imparting propertyis due to molecule's chemical structure, the only way to remove oreliminate the color is to remove the molecules or alter their chemicalstructure. More recently, methods of imparting “structural color” toman-made objects have been developed. Structural color is color which isproduced, at least in part, by microscopically structured surfaces thatinterfere with visible light contacting the surface. The structuralcolor is color caused by physical phenomena including the scattering,refraction, reflection, interference, and/or diffraction of light,unlike color caused by the absorption or emission of visible lightthrough coloring matters. For example, optical phenomena which impartstructural color can include single- or multi-layer interference,thin-film interference, refraction, dispersion, light scattering, Miescattering, diffraction, and diffraction grating. As structural color isproduced by physical structures, destroying or altering the physicalstructures can eliminate or alter the imparted color. The ability toeliminate color by destroying the physical structure, such as bygrinding or melting an article can facilitate recycling and reusecolored materials. In various aspects described herein, achromaticstructural color imparted to an article can be visible to an observerhaving 20/20 visual acuity and normal color vision from a distance ofabout 1 meter from the article, when the structurally-colored region isilluminated by about 30 lux of sunlight, incandescent light, orfluorescent light. In some such aspects, the structurally-colored regionis at least one square centimeter in size.

As described herein, achromatic structural color is produced, at leastin part, by the optical element, as opposed to the color being producedsolely by pigments and/or dyes. The coloration of an article can be duesolely to achromatic structural color (i.e., the article, a coloredportion of the article, or a colored outer layer of the article can besubstantially free of pigments and/or dyes). Achromatic structural colorcan also be used in combination with pigments and/or dyes, for example,to alter all or a portion of the achromatic structural color.

In another aspect, the optical element can impart a “combined achromaticcolor,” where a “combined achromatic color” can be described as having astructural color component and a non-structural color component. Forexample, achromatic structural color can be used in combination withpigments and/or dyes to alter all or a portion of the achromaticstructural color, forming a combined achromatic structural color. In acombined achromatic color, the structural color component, when viewedwithout the non-structural color component, imparts a structural colorhaving a first achromatic color and the non-structural color component,when viewed without the structural color component imparts a secondachromatic color, where the first achromatic structural color and thesecond achromatic color differ. Further in this aspect, when viewedtogether, the first achromatic structural color and the secondachromatic color combine to form a third, combined achromatic color,which differs from either the first achromatic structural color or thesecond achromatic color, for example, through shifting the reflectancespectrum of the optical element.

In another aspect, an optical element can impart a “modified achromaticcolor,” where a “modified achromatic color” can be described as havingan achromatic structural color component and a modifier component. In amodified achromatic color, the achromatic structural color component,when viewed without the modifier component, imparts an achromaticstructural color and the modifier component, when viewed without thestructural color component, does not impart any color, hue, or chroma.Further in this aspect, when viewed together, the modifier component canexpand, narrow, or shift the range of wavelengths of light reflected orabsorbed by the structural color component. In still another aspect, anoptical element can impart a “modified combined achromatic color,” wherea “modified combined achromatic color” can be described has having astructural color component having a first achromatic structural color, anon-structural color component having a second achromatic color, and amodifier component not imparting a color but instead functioning toexpand, narrow, or shift the range of wavelengths of light reflected bythe combined achromatic color formed from the structural color componentand the non-structural color component.

In one aspect, the structural color component, combined color component,or modified color component disclosed herein is opaque; that is, itprevents light from passing through any articles to which they areapplied. Further in this aspect, most wavelengths of light are absorbedo reflected by one or more layers of the structural color, combinedcolor, or modified color component.

“Hue” is commonly used to describe the property of color which isdiscernible based on a dominant wavelength(s) of visible light, and isoften described using terms such as magenta, red, orange, yellow, green,cyan, blue, indigo, violet, etc. or can be described in relation (e.g.,as similar or dissimilar) to one of these. The hue of a color isgenerally considered to be independent of the intensity or lightness ofthe color. For achromatic color, the hue is typically zero and lightnessimparts the white, black, or gray color (or shade). For example, in theMunsell color system, the properties of color include hue, value(lightness) and chroma (color purity), where for achromatic color hueand chroma are not present or present at very low levels so one viewingthe color perceives it as achromatic structural color. Particular huesare commonly associated with particular ranges of wavelengths in thevisible spectrum: wavelengths in the range of about 700 to 635nanometers are associated with red, the range of about 635 to 590nanometers is associated with orange, the range of about 590 to 560nanometers is associated with yellow, the range of about 560 to 520nanometers is associated with green, the range of about 520 to 490nanometers is associated with cyan, the range of about 490 nanometers to450 nanometers is associated with blue, and the range of about 450 to400 nanometers is associated with violet. As described herein, thatachromatic color can have no hue or chroma and the achromatic color is acolor in which no particular wavelength, hue and/or chroma predominates,where for wavelength all wavelengths are present in equal parts orsubstantially equal parts. The achromatic color can be selected fromblack, white, or neutral gray and shades therein. The wavelength rangecan be about 380 to 740 nanometers and can be measured as a function ofabsorbance or reflectance, each of which can be used to define theachromatic structural color imparted by the optical element.

While the optical element may impart a first achromatic structuralcolor, the presence of an optional textured surface and/or primer layercan alter the achromatic structural color or in the alternative have noimpact on the first achromatic structural color. Other factors such ascoatings or transparent elements may further alter the perceivedachromatic structural color.

In some embodiments, the achromatic structural color of astructurally-colored article does not change substantially, if at all,depending upon the angle at which the article is observed orilluminated. In instances such as this the achromatic structural colorcan be angle-independent or when observed is substantially independentor is independent of the angle of observation.

Other factors such as coatings or transparent elements may further alterthe perceived achromatic structural color. The achromatic structuralcolor can be referred to as a “non-shifting” (i.e., the achromatic colorremains substantially the same, regardless of the angle of observationand/or illumination), or “shifting” (i.e., the achromatic color variesdepending upon the angle of observation and/or illumination (e.g.,shifts from black to gray, shifts from gray to white, shifts from blackto white, shifts between different shades of gray, shifts betweendifferent shades of white, shifts between different shades of black, andthe like)). The shifting achromatic color can change gradually over twoor more shades as the angle of observation or illumination changes(e.g., a change of across 2 to 15, 2 to 10, 5 to 15, 2 to 8, or 2 to 6degrees) or can shift from a first achromatic color to a secondachromatic color upon reaching a threshold change (e.g., an abruptchange) in angle of observation or illumination (e.g., an change of 1-5or 1-3, or 1-2 degrees). The shifting of the achromatic structural colorcan change gradually across white-gray-black or across a narrower shift(e.g., across shades of gray, black to gray, gray to white) as the angleof observation or illumination changes. The shifting achromaticstructural color can change more abruptly between a limited number ofshades (e.g., between 2-8, or between 2-4, or between 2) as the angle ofobservation or illumination changes. The achromatic structural color canbe a shifting achromatic structural color in which two or moreachromatic colors are imparted by the achromatic structural color. Theachromatic structural color can further be a shifting achromaticstructural color in which the achromatic structural color varies over awide number (e.g., 6, 7, 8 or more achromatic colors) when viewed at asingle viewing angle, or when viewed from two or more different viewingangles that are at least 10 degree or at least 15 degrees apart fromeach other. The shifting is not iridescent.

As discussed above, the color of an achromatic structurally-coloredarticle (e.g., an article include achromatic structural color) can beindependent of or vary depending upon the angle at which thestructurally-colored article is observed or illuminated. As used herein,the “angle” of illumination or viewing is the angle measured from anaxis or plane that is orthogonal to the surface. The viewing orilluminating angles can be set between about 0 and 180 degrees (as wellas within increments of 1 degree therein). The viewing or illuminatingangles can be set at 0 degrees, 5 degrees, 10 degrees, 15 degrees, 30degrees, 45 degrees, 60 degrees, and −15 degrees and the color can bemeasured using a colorimeter or spectrophotometer (e.g., KonicaMinolta), which focuses on a particular area of the article to measurethe color. The viewing or illuminating angles can be set at 0 degrees, 5degrees, 10 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, 75degrees, 90 degrees, 105 degrees, 120 degrees, 135 degrees, 150 degrees,165 degrees, 180 degrees, 195 degrees, 210 degrees, 225 degrees, 240degrees, 255 degrees, 270 degrees, 285 degrees, 300 degrees, 315degrees, 330 degrees, and 345 degrees and the color can be measuredusing a colorimeter or spectrophotometer

Various methodologies for defining color coordinate systems exist. Oneexample is L*a*b* color space, where, for a given illuminationcondition, L* is a value for lightness, and a* and b* are values forcolor-opponent dimensions based on the CIE coordinates (CIE 1976 colorspace or CIELAB) (e.g., a* and b* are 0 or close to 0). In anembodiment, an achromatic structural color can be considered as having a“single” achromatic color when the change in achromatic color measuredfor the article is within about 10 percent or within about 5 percent ofthe total scale of the a* or b* coordinate of the L*a*b* scale (CIE 1976color space) at three or more measured observation or illuminationangles selected from measured at observation or illumination angles of 0degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and −15degrees.

Another example of a color scale is the CIELCH color space, where, for agiven illumination condition, L* is a value for lightness, C* is a valuefor chroma, and h° denotes a hue as an angular measurement (e.g., C* andh° are 0 or close to 0). In an embodiment, a structural color can beconsidered as having a “single” color when the color measured for thearticle is less than 10 degrees different or less than 5 degreesdifferent at the h° angular coordinate of the CIELCH color space, atthree or more measured observation or illumination angles selected frommeasured at observation or illumination angles of 0 degrees, 15 degrees,30 degrees, 45 degrees, 60 degrees, and −15 degrees. In certainembodiments, colors which, when measured and assigned values in theCIELCH system that vary by at least 45 degrees in the h° measurements,are considered to be different colors

Another system for characterizing color includes the “PANTONE” MatchingSystem (Pantone LLC, Carlstadt, N.J., USA), which provides a visualcolor standard system to provide an accurate method for selecting,specifying, broadcasting, and matching colors through any medium. In anexample, a first optical element and a second optical element can besaid to have the same achromatic color when the achromatic colormeasured for each optical element is within a certain number of adjacentstandards, e.g., within 20 adjacent PANTONE standards, at three or moremeasured observation or illumination angles selected from 0 degrees, 15degrees, 30 degrees, 45 degrees, 60 degrees, and 75 degrees. In analternative aspect, the first optical element and the second opticalelement can be said to have different achromatic colors when theachromatic color measured for each optical element is outside a certainnumber of adjacent standards, e.g., at least 20 adjacent PANTONEstandards or farther apart, at three or more measured observation orillumination angles selected from 0 degrees, 15 degrees, 30 degrees, 45degrees, 60 degrees, and 75 degrees. In another aspect, an opticalelement can be said to be single-achromatic color when all areas of theoptical element have the same PANTONE color as defined herein, or can bemulti-achromatic colored when at least two areas of the optical elementhave different PANTONE colors. In another aspect, a single opticalelement can be said to have a non-shifting achromatic color if itexhibits the same PANTONE color as defined herein at three or moremeasured observation or illumination angles (e.g., 0 degrees, 15degrees, 30 degrees, 45 degrees, 60 degrees, and −15 degrees). In analternative aspect, a single optical element can be said to be shiftingif it exhibits two, three, or four different PANTONE achromatic colorsas defined herein at two or more measured observation or illuminationangles (e.g., 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees,and −15 degrees).

Another example of a color scale is the Natural Color System® or NCS,which is built on principles of human physiological vision and describescolor by using color similarity relationships. The NCS is based on thepremise that the human visual system consists of six elementary colorprecepts, or colors that can be challenging to define perceptually interms of other colors. These colors consist of three pairs: (i) theachromatic colors of black (S) and white (W), (ii) the opposing primarycolor pair of red (R) and green (G), and (iii) the opposing primarycolor pair of yellow (Y) and blue (B). In the NCS, any color that can beperceived by the human eye can be similar to the two achromatic colorsand a maximum of two non-opposing primary colors. Thus, for example, aperceived color can have similarities to red and blue but not to red andgreen. NCS descriptions of colors are useful for colors that belong tothe surfaces of materials, so long as the surfaces are not fluorescent,translucent, luminescent, or the like; the NCS does not encompass othervisual properties of the surface such as, for example, gloss andtexture.

The NCS color space is a three dimensional model consisting of a flatcircle at which the four primary colors are positioned in order at 0degrees, 90 degrees, 180 degrees, and 270 degrees. For example, ifyellow is at 0 degrees, red is at 90 degrees, blue is at 180 degrees,and green is at 270 degrees. White is represented above the circle andblack below such that a hue triangle forms between the black/white(grayscale) axis and any point on the circle.

Percentage “blackness” (s) is defined in the NCS as a color's similarityto the elementary color black. Percentage “chromaticness” (c) representssimilarity to the most saturated color in a hue triangle. “Hue” (ϕ) inthe NCS, meanwhile, represents similarity of a color to one or at mosttwo non-opposing primary colors. Blackness and chromaticness add up to avalue less than or equal to 100 percent; any remaining value is referredto as “whiteness” (w) of a color. In some cases, the NCS can be used tofurther describe “saturation” (m), a value from 0 to 1 determined interms of chromaticness and whiteness (e.g., m=c/(w+c)). NCS can furtherbe used to describe “lightness” (v), a description of whether the colorcontains more of the achromatic elementary colors black or white. A pureblack article would have a lightness of 0 and a pure white article wouldhave a lightness of 1. Purely neutral grays (c=0) have lightness definedby v=(100−s)/100, while chromatic colors are first compared to areference scale of grays and lightness is then calculated as for grays.

NCS notation takes the generic form sc-AϕB, where sc defines “nuance,”ss is the percent blackness and cc refers to the chromaticity; A and Bare the two primary colors to which the color relates; and ϕ is ameasure of where a color falls between A and B. Thus, a color (e.g.,orange) that has equal amounts of yellow and red could be representedsuch that AϕB=Y50R (e.g., yellow with 50 percent red), whereas a colorhaving relatively more red than yellow is represented such thatAϕB=Y60R, Y70R, Y80R, Y90R, or the like. The color having equal amountsof yellow and red with a relatively low (10 percent) amount of darknessand a medium (50 percent) level of chromaticity would thus berepresented as 1050-Y50R. In this system, neutral colors having noprimary color components are represented by sc-N, where sc is defined inthe same manner as with a non-neutral color and N indicates neutrality,while a pure color would have a notation such as, for example, 3050-B(for a blue with 30 percent darkness and 50 percent chromaticity). Acapital “S” in front of the notation indicates that a value was presentin the NCS 1950 Standard, a reduced set of samples. As of 2004, the NCSsystem contains 1950 standard colors.

The NCS is more fully described in ASTM E2970-15, “Standard Practice forSpecifying Color by the Natural Colour System (NCS).” Although the NCSis based on human perception and other color scales such as the CI ELABor CIELCH spaces may be based on physical properties of objects, NCS andCIE tristimulus values are interconvertible.

In an example, a first optical element and a second optical element canbe considered as being the same achromatic color when the achromaticcolors measured for each optical element are within a certain number ofadjacent standards, e.g., within 20 adjacent NCS values, at three ormore measured observation or illumination angles selected from 0degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and −15degrees. In another example, the first optical element and the secondoptical element can be considered as being different achromatic colorswhen the colors measured for each optical element are outside a certainnumber of adjacent standards, e.g., farther apart than at least 20adjacent NCS values, at three or more measured observation orillumination angles selected from 0 degrees, 15 degrees, 30 degrees, 45degrees, 60 degrees, and −15 degrees. In another aspect, an opticalelement can be said to be a single achromatic color when all areas ofthe optical element have the same NCS color as defined herein, or can bemulti-achromatic colored when at least two areas of the optical elementhave different NCS colors. In another aspect, a single optical elementcan be said to have a non-shifting achromatic color if it exhibits thesame NCS color as defined herein at three or more measured observationor illumination angles (e.g., 0 degrees, 15 degrees, 30 degrees, 45degrees, 60 degrees, and −15 degrees). In an alternative aspect, asingle optical element can be said to be shifting achromatic color if itexhibits two, three, or four different NCS colors as defined herein attwo or more measured observation or illumination angles (e.g., 0degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and −15degrees).

The method of making articles including the optical element (e.g.,structurally colored article) can include disposing (e.g., affixing,attaching, bonding, fastening, joining, appending, connecting, binding)the optical element onto an article (e.g., an article of footwear, anarticle of apparel, an article of sporting equipment, etc.). The articleincludes a component, and the component has a surface upon which theoptical element can be disposed. The surface of the article can be madeof a material such as a thermoplastic material or thermoset material, asdescribed herein. For example, the article has a surface including athermoplastic material (i.e., a first thermoplastic material), forexample an externally-facing surface of the component or aninternally-facing surface of the component (e.g., an externally-facingsurface or an internally-facing surface a bladder). The optical elementcan be disposed onto the thermoplastic material, for example.

In an aspect, the temperature of at least a portion of the first surfaceof the article including the thermoplastic material is increased to atemperature at or above creep relaxation temperature (Tcr), Vicatsoftening temperature (Tvs), heat deflection temperature (Thd), and/ormelting temperature (Tm) of the thermoplastic material, for example tosoften or melt the thermoplastic material. The temperature can beincreased to a temperature at or above the creep relaxation temperature.The temperature can be increased to a temperature at or above the Vicatsoftening temperature. The temperature can be increased to a temperatureat or above the heat deflection temperature. The temperature can beincreased to a temperature at or above the melting temperature. Whilethe temperature of the at least a portion of the first side of thearticle is at or above the increased temperature (e.g., at or above thecreep relaxation temperature, the heat deflection temperature, the Vicatsoftening temperature, or the melting temperature of the thermoplasticmaterial), the optical element is affixed to the thermoplastic materialwithin the at least a portion of the first side of the article.Following the affixing, the temperature of the thermoplastic material isdecreased to a temperature below its creep relaxation temperature to atleast partially re-solidify the thermoplastic material. Thethermoplastic material can be actively cooled (e.g., removing the sourcethat increases the temperature and actively (e.g., flowing cooler gasadjacent the article reducing the temperature of the thermoplasticmaterial) or passively cooled (e.g., removing the source that increasesthe temperature and allowing the thermoplastic layer to cool on itsown).

The method of making the article can include disposing (e.g., affixing,attaching, bonding, fastening, joining, appending, connecting, binding,which includes operably disposing etc.) the optical element onto asurface of an article (e.g., an article of footwear, an article ofapparel, an article of sporting equipment, etc.) or a surface of acomponent of an article. The article can include a component, and thecomponent can include the surface upon which the optical element is bedisposed. The surface of the article can be made of a material such as athermoplastic material or thermoset material, as described herein. Forexample, the article can have a surface including a thermoplasticmaterial (i.e., a first thermoplastic material), for example anexternally-facing surface of the component or article or aninternally-facing surface of the component or article (e.g., anexternally-facing surface or an internally-facing surface a bladder).The optical element can be disposed onto the thermoplastic material, forexample.

Now having described color and other aspects generally, additionaldetails regarding the optical element are provided. As described herein,the article includes the optical element. The optical element caninclude at least one reflective layer (e.g., base and/or non-basereflective layers) and/or at least one constituent layer. The opticalelement that can be or include a single or multilayer reflector or amultilayer filter. The optical element can function to modify the lightthat impinges thereupon so that achromatic structural color is impartedto the article. The optical element can also optionally include one ormore additional layers (e.g., a protective layer, the textured layer, apolymer layer, and the like). The optical element can have a thicknessof about 100 to about 1,500 nanometers, about 100 to about 1,200nanometers, about 100 to about 700 nanometers, or of about 200 to about500 nanometers.

The optical element can be an optical element, an organic opticalelement, or a mixed inorganic/organic optical element, where the layers(e.g., reflective layer, constituent layer) can be made of these typesof materials. The organic optical element has at least one layer andthat layer is made of an organic material. The organic material caninclude a polymer, such as those described herein. The organic materialis made of a non-metal or non-metal oxide material. The organic materialthat does not include a metal or metal oxide. The organic material ismade of a polymeric material that does not include a metal or metaloxide.

The inorganic optical element has at least one layer and that layer ismade of a non-organic material. As described in detail herein, thenon-organic material can be a metal or metal oxide. The non-organicmaterial does not include any organic material.

The optical element can be a mixed inorganic/organic optical element,meaning that one or more of the layers can be made of an inorganicmaterial, one or more layers can be made of an organic material, and/orone or more layers can be made of a layer of a mixture of inorganic andorganic materials (e.g., a polymer include metal or metal oxideparticles (e.g., micro- or nano-particles).

The optical element has a first side (including the outer surface) and asecond side opposing the first side (including the opposing outersurface), where the first side or the second side is adjacent thearticle. For example, when the optical element is used in conjunctionwith a component having internally-facing and externally-facingsurfaces, such as a film or a bladder, the first side of the opticalelement can be disposed on the internally-facing surface of thecomponent, such as in the following order: second side of the opticalelement/core of the optical element/first side of the opticalelement/internally-facing surface of the component/core of thecomponent/externally-facing surface of the component. Alternatively, thesecond side the optical element can be disposed on the internally-facingsurface of the component, such as in the following order: first side ofthe optical element/core of the optical element/second side of theoptical element/internally-facing surface of the component/core of thecomponent wall/externally-facing surface of the component. In anotherexample, the first side of the optical element can be disposed on theexternally-facing surface of the component, such as in the followingorder: internally-facing surface of the component/core of thecomponent/externally-facing surface of the component/first side of theoptical element/core of the optical element/second side of the opticalelement. Similarly, the second side of the optical element can bedisposed on the externally-facing surface of the component, such as inthe following order: internally-facing surface of the component/core ofthe component/externally-facing surface of the component/second side ofthe optical element/core of the optical element/first side of theoptical element. In examples where the optional textured surface, thetextured surface can be located at the interface between the surface ofthe component and a side of the optical element.

In regard to the components of the optical element, when the opticalelement is on and visible from an outside surface of the article, thebase reflective layer is between the at least two constituent layers andthe surface. When the optical element is on an inside surface of thearticle and is visible through an outside surface of the article, the atleast two constituent layers are between the base reflective layer andthe surface.

The optical element or layers or portions thereof (e.g., reflectivelayer, constituent layer) can be formed using known techniques such asphysical vapor deposition, electron beam deposition, atomic layerdeposition, molecular beam epitaxy, cathodic arc deposition, pulsedlaser deposition, sputtering deposition (e.g., radio frequency, directcurrent, reactive, non-reactive), chemical vapor deposition,plasma-enhanced chemical vapor deposition, low pressure chemical vapordeposition and wet chemistry techniques such as layer-by-layerdeposition, sol-gel deposition, Langmuir blodgett, and the like. Thetemperature of the first side can be adjusted using the technique toform the optical element and/or a separate system to adjust thetemperature.

The optical element can comprise a single layer a multilayer reflector(e.g., reflective layer(s) and/or constituent layer(s)). The singlelayer filter or multilayer reflector can be configured to have a certainreflectivity for a range of wavelengths depending, at least in part, onthe material selection, thickness and number of the layers of themultilayer reflector. In other words, one can carefully select thematerials, thicknesses, and numbers of the layers of a multilayerreflector and optionally its interaction with one or more other layers,so that it can reflect and/or absorb a wavelength range of light toproduce a desired achromatic structural color.

The optical element can include at least one reflective layer and/or atleast two adjacent constituent layers, where the adjacent constituentlayers (e.g., and the non-base reflective layer(s) when present) havedifferent refractive indices. The difference in the index of refractionof adjacent layers of the constituent layer, and the reflective layerwhen present, can be about 0.0001 to about 50 percent, about 0.1 toabout 40 percent, about 0.1 to about 30 percent, about 0.1 to about 20percent, about 0.1 to about 10 percent (and other ranges there between(e.g., the ranges can be in increments of 0.0001 to 5 percent)). Theindex of refraction depends at least in part upon the material of theconstituent and can range from about 1.3 to about 2.6.

The combination of the reflective(s) layer and/or the constituentlayer(s) can include 2 to 20 layers, 2 to 15, 2 to 10 layer, 2 to 6layers, or 2 to 4 layers. Each of the reflective layer(s) or theconstituent layer(s) can have a thickness that is about one-fourth ofthe wavelength of light to be reflected to produce the desiredachromatic structural color. Each of the reflective layer(s) or theconstituent layer(s) can have a thickness of about 10 to about 500nanometers or about 90 to about 200 nanometers. The optical element canhave at least two constituent layers, where adjacent constituent layershave different thicknesses and optionally the same or differentrefractive indices.

The optical element can comprise a single layer filter or a multilayerfilter. The single layer filter or the multilayer filter destructivelyinterferes with light that impinges upon the article, where thedestructive interference of the light and optionally interaction withone or more other layers or structures of the optical element (e.g., amultilayer reflector, a textured structure) impart the achromaticstructural color. In this regard, the layers of the multilayer filtercan be designed (e.g., material selection, thickness, number of layer,and the like) so that certain wavelength range is reflected and/orabsorbed to a certain degree to impart the desired achromatic structuralcolor.

The reflective layer(s) and/or constituent layer(s) can include multiplelayers where each layer independently comprises a material selectedfrom: the transition metals, the metalloids, the lanthanides, and theactinides, as well as oxides, nitrides, oxynitrides, sulfides, sulfates,selenides, and tellurides of these, as well as stainless steel andothers described herein. The reflective layer(s) and/or constituentlayer(s) can be titanium, aluminum, silver, zirconium, chromium,magnesium, silicon, gold, platinum, stainless steel, and a combinationthereof as well as oxides of each. The material for the constituentlayer(s) can be selected to provide an index of refraction that whenoptionally combined with the other layers of the optical elementachieves the desired result. One or more layers of the constituent layercan be made of liquid crystals. Each layer of the constituent layer canbe made of liquid crystals. One or more layers of the constituent layercan be made of a material such as: silicon dioxide, titanium dioxide,zinc sulfide, magnesium fluoride, tantalum pentoxide, aluminum oxide, ora combination thereof. Each layer of the constituent layer can be madeof a material such as: silicon dioxide, titanium dioxide, zinc sulfide,magnesium fluoride, tantalum pentoxide, aluminum oxide, or a combinationthereof. To improve adhesion between layers, a metal layer is adjacent ametal oxide layer comprising the same metal. For example, Ti and TiO_(x)(e.g., x is 1 to 2) can be positioned adjacent one another to improveadhesion.

The optical element can be uncolored (e.g., no pigments or dyes added tothe structure or its layers), colored (e.g., pigments and/or dyes areadded to the structure or its layers. The surface of the component uponwhich the optical element is disposed can be uncolored (e.g., nopigments or dyes added to the material), colored (e.g., pigments and/ordyes are added to the material), reflective, and/or transparent (e.g.,percent transmittance of about 75 percent or more).

The reflective layer(s) and/or the constituent layer(s) can be formed ina layer-by-layer manner, where each layer has a different index ofrefraction. Each layer can have a textured topography or a threedimensional flat planar surface or substantially three dimensional flatplanar surface. Each of the reflective layer(s) and/or the constituentlayer(s) can be formed using known techniques such as those describedabove and herein.

As mentioned above, the optical element can include one or more layersin addition to the reflective layer(s) and the constituent layer(s). Theoptical element has a first side (e.g., the side having a surface) and asecond side (e.g., the side having a surface), where the first side orthe second side is adjacent the surface of the component. The one ormore other layers of the optical element can be on the first side and/orthe second side of the optical element. For example, the optical elementcan include the top layer (e.g., non-stoichiometric metal layer), aprotective layer and/or a polymeric layer such as a thermoplasticpolymeric layer, where the protective layer and/or the polymeric layercan be on one or both of the first side and the second side of theoptical element. One or more of the optional other layers can include atextured surface. Alternatively or in addition, one or more of thereflective layer(s) and/or one or more constituent layer(s) of theoptical element can include a textured surface.

A protective layer can be disposed on the first and/or second side ofthe constituent layer to protect the constituent layer. The protectivelayer is more durable or more abrasion resistant than the constituentlayer. The protective layer is optically transparent to visible light.The protective layer can be on the first side of the optical element toprotect the constituent layer. All or a portion of the protective layercan include a dye or pigment in order to alter an appearance of theachromatic structural color. The protective layer can include silicondioxide, glass, combinations of metal oxides, or mixtures of polymers.The protective layer can have a thickness of about 3 nanometers to about1 millimeter.

The protective layer can be formed using physical vapor deposition,chemical vapor deposition, pulsed laser deposition, evaporativedeposition, sputtering deposition (e.g., radio frequency, directcurrent, reactive, non-reactive), plasma enhanced chemical vapordeposition, electron beam deposition, cathodic arc deposition, lowpressure chemical vapor deposition and wet chemistry techniques such aslayer by layer deposition, sol-gel deposition, Langmuir blodgett, andthe like. Alternatively or in addition, the protective layer can beapplied by spray coating, dip coating, brushing, spin coating, doctorblade coating, and the like.

A polymeric layer can be disposed on the first and/or the second side ofthe optical element. The polymeric layer can be used to dispose theoptical element onto an article, such as, for example, when the articledoes not include a thermoplastic material to adhere the optical element.The polymeric layer can comprise a polymeric adhesive material, such asa hot melt adhesive. The polymeric layer can be a thermoplastic materialand can include one or more layers. The thermoplastic material can beany one of the thermoplastic material described herein. The polymericlayer can be applied using various methodologies, such as spin coating,dip coating, doctor blade coating, and so on. The polymeric layer canhave a thickness of about 3 nanometer to about 1 millimeter.

As described above, one or more embodiments of the present disclosureprovide articles that incorporate the optical element (e.g., single ormultilayer structures) on a side of a component of the article to impartachromatic structural color. The optical element can be disposed ontothe thermoplastic material of the side of the article, and the side ofthe article can include a textile, including a textile comprising thethermoplastic material.

Having described aspects, additional details will now be described forthe optional textured surface. As described herein, the componentincludes the optical element and the optical element can include atleast one reflective layer and/or at least one constituent layer andoptionally a textured surface. The textured surface can be a surface ofa textured structure or a textured layer. The textured surface may beprovided as part of the optical element. For example, the opticalelement may comprise a textured layer or a textured structure thatcomprises the textured surface. The textured surface may be formed onthe first or second side of the optical element. For example, a side ofthe reflective layer and/or the constituent layer may be formed ormodified to provide a textured surface, or a textured layer or texturedstructure can be affixed to the first or second side of the opticalelement. The textured surface may be provided as part of the componentto which the optical element is disposed. For example, the opticalelement may be disposed onto the surface of the component where thesurface of the component is a textured surface, or the surface of thecomponent includes a textured structure or a textured layer affixed toit.

The textured surface (or a textured structure or textured layerincluding the textured surface) may be provided as a feature on or partof another medium, such as a transfer medium, and imparted to a side orlayer of the optical element or to the surface of the component. Forexample, a mirror image or relief form of the textured surface may beprovided on the side of a transfer medium, and the transfer mediumcontacts a side of the optical element or the surface of the componentin a way that imparts the textured surface to the optical element orarticle. While the various embodiments herein may be described withrespect to a textured surface of the optical element, it will beunderstood that the features of the textured surface, or a texturedstructure or textured layer, may be imparted in any of these ways.

The textured surface can contribute to the achromatic structural colorresulting from the optical element or may not contribute to theachromatic structural color. As described herein, achromatic structuralcoloration is imparted, at least in part, due to optical effects causedby physical phenomena such as scattering, diffraction, reflection,interference or unequal refraction of light rays from an opticalelement. The textured surface (or its mirror image or relief) caninclude a plurality of profile features and flat or planar areas. Theplurality of profile features included in the textured surface,including their size, shape, orientation, spatial arrangement, etc., canaffect the light scattering, diffraction, reflection, interferenceand/or refraction resulting from the optical element. The flat or planarareas included in the textured surface, including their size, shape,orientation, spatial arrangement, etc., can affect the light scattering,diffraction, reflection, interference and/or refraction resulting fromthe optical element. The desired achromatic structural color can bedesigned, at least in part, by adjusting one or more of properties ofthe profile features and/or flat or planar areas of the texturedsurface.

The profile features can extend from a side of the flat areas, so as toprovide the appearance of projections and/or depressions therein. A flatarea can be a flat planar area. A profile feature may include variouscombinations of projections and depressions. For example, a profilefeature may include a projection with one or more depressions therein, adepression with one or more projections therein, a projection with oneor more further projections thereon, a depression with one or morefurther depressions therein, and the like. The flat areas do not have tobe completely flat and can include texture, roughness, and the like. Thetexture of the flat areas may not contribute much, if any, to theimparted achromatic structural color. The texture of the flat areastypically contributes to the imparted achromatic structural color. Forclarity, the profile features and flat areas are described in referenceto the profile features extending above the flat areas, but the inverse(e.g., dimensions, shapes, and the like) can apply when the profilefeatures are depressions in the textured surface.

The textured surface can comprise a thermoplastic material. The profilefeatures and the flat areas can be formed using a thermoplasticmaterial. For example, when the thermoplastic material is heated aboveits softening temperature a textured surface can be formed in thethermoplastic material such as by molding, stamping, printing,compressing, cutting, etching, vacuum forming, etc., the thermoplasticmaterial to form profile features and flat areas therein. The texturedsurface can be imparted on a side of a thermoplastic material. Thetextured surface can be formed in a layer of thermoplastic material. Theprofile features and the flat areas can be made of the samethermoplastic material or a different thermoplastic material.

The textured surface generally has a length dimension extending along anx-axis, and a width dimension extending along a z-axis, and a thicknessdimension extending along a y-axis. The textured surface has a generallyplanar portion extending in a first plane that extends along the x-axisand the z-axis. A profile feature can extend outward from the firstplane, so as to extend above or below the plane x. A profile feature mayextend generally orthogonal to the first plane, or at an angle greaterto or less than 90 degrees to the first plane.

The dimensional measurements in reference to the profile features (e.g.,length, width, height, diameter, and the like) described herein refer toan average dimensional measurement of profile features in 1 squarecentimeter in the optical element.

The dimension (e.g., length, width, height, diameter, depending upon theshape of the profile feature) of each profile feature can be within thenanometer to micrometer range. A textured surface can have a profilefeature and/or flat area with a dimension of about 10 nanometers toabout 500 micrometers. The profile feature can have dimensions in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. All of the dimensions of the profile feature (e.g., length,width, height, diameter, depending on the geometry) can be in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. The textured surface can have a plurality of profilefeatures having dimensions that are 1 micrometer or less. In thiscontext, the phrase “plurality of the profile features” is meant to meanthat about 50 percent or more, about 60 percent or more, about 70percent or more, about 80 percent or more, about 90 percent or more, orabout 99 percent or more of the profile features have a dimension inthis range. The profile features can have a ratio of width:height and/orlength:height dimensions of about 1:2 and 1:100, or 1:5 and 1:50, or 1:5and 1:10.

The textured surface can have a profile feature and/or flat area with adimension within the micrometer range of dimensions. A textured surfacecan have a profile feature and/or flat area with a dimension of about 1micrometer to about 500 micrometers. All of the dimensions of theprofile feature (e.g., length, width, height, diameter, depending on thegeometry) can be in the micrometer range, e.g., from about 1 micrometerto about 500 micrometers. The textured surface can have a plurality ofprofile features having dimensions that are from about 1 micrometer toabout 500 micrometer. In this context, the phrase “plurality of theprofile features” is meant to mean that about 50 percent or more, about60 percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have a dimension in this range. The height of the profilefeatures (or depth if depressions) can be about 0.1 and 50 micrometers,about 1 to 5 micrometers, or 2 to 3 micrometers. The profile featurescan have a ratio of width:height and/or length:height dimensions ofabout 1:2 and 1:100, or 1:5 and 1:50, or 1:5 and 1:10.

A textured surface can have a plurality of profile features having amixture of size dimensions within the nanometer to micrometer range(e.g., a portion of the profile features are on the nanometer scale anda portion of the profile features are on the micrometer scale). Atextured surface can have a plurality of profile features having amixture of dimensional ratios. The textured surface can have a profilefeature having one or more nanometer-scale projections or depressions ona micrometer-scale projection or depression.

The profile feature can have height and width dimensions that are withina factor of three of each other (0.33 w≤h≤3 w where w is the width and his the height of the profile feature) and/or height and lengthdimensions that are within a factor of three of each other (0.33 l≤h≤3lwhere l is the length and h is the height of the profile feature). Theprofile feature can have a ratio of length:width that is from about 1:3to about 3:1, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1,or about 1:1.2 to about 1.2:1, or about 1:1. The width and length of theprofile features can be substantially the same or different.

In another aspect, the textured surface can have a profile featureand/or flat area with at least one dimension in the mid-micrometer rangeand higher (e.g., greater than 500 micrometers). The profile feature canhave at least one dimension (e.g., the largest dimension such as length,width, height, diameter, and the like depending upon the geometry orshape of the profile feature) of greater than 500 micrometers, greaterthan 600 micrometers, greater than 700 micrometers, greater than 800micrometers, greater than 900 micrometers, greater than 1000micrometers, greater than 2 millimeters, greater than 10 millimeters, ormore. For example, the largest dimension of the profile feature canrange from about 600 micrometers to about 2000 micrometers, or about 650micrometers to about 1500 micrometers, or about 700 micrometers to about1000 micrometers. At least one or more of the dimensions of the profilefeature (e.g., length, width, height, diameter, depending on thegeometry) can be in the micrometer range, while one or more of the otherdimensions can be in the nanometer to micrometer range (e.g., less than500 micrometers, less than 100 micrometers, less than 10 micrometers, orless than 1 micrometer). The textured surface can have a plurality ofprofile features having at least one dimension that is in themid-micrometer or more range (e.g., 500 micrometers or more). In thiscontext, the phrase “plurality of the profile features” is meant to meanthat about 50 percent or more, about 60 percent or more, about 70percent or more, about 80 percent or more, about 90 percent or more, orabout 99 percent or more of the profile features have at least onedimension that is greater than 500 micrometers. In particular, at leastone of the length and width of the profile feature is greater than 500micrometers or both the length and the width of the profile feature isgreater than 500 micrometers. In another example, the diameter of theprofile feature is greater than 500 micrometers. In another example,when the profile feature is an irregular shape, the longest dimension isgreater than 500 micrometers.

In aspects, the height of the profile features can be greater than 50micrometers. In this context, the phrase “plurality of the profilefeatures” is meant to mean that about 50 percent or more, about 60percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have at height that is greater than 50 micrometers. The heightof the profile feature can be 50 micrometers, about 60 micrometers,about 70 micrometers, about 80 micrometers, about 90 micrometers, orabout 100 micrometers to about 60 micrometers, about 70 micrometers,about 80 micrometers, about 90 micrometers, about 100 micrometers, about150 micrometers, about 250 micrometers, about 500 micrometers or more.For example, the ranges can include 50 micrometers to 500 micrometers,about 60 micrometers to 250 micrometers, about 60 micrometers to about150 micrometers, and the like. One or more of the other dimensions(e.g., length, width, diameter, or the like) can be in the nanometer tomicrometer range (e.g., less than 500 micrometers, less than 100micrometers, less than 10 micrometers, or less than 1 micrometer). Inparticular, at least one of the length and width of the profile featureis less than 500 micrometers or both the length and the width of theprofile feature is less than 500 micrometers, while the height isgreater than 50 micrometers. One or more of the other dimensions (e.g.,length, width, diameter, or the like) can be in the micrometer tomillimeter range (e.g., greater than 500 micrometers to 10 millimeters).

The dimension (e.g., length, width, height, diameter, depending upon theshape of the profile feature) of each profile feature can be within thenanometer to micrometer range. The textured surface can have a profilefeature and/or flat area with a dimension of about 10 nanometers toabout 500 micrometers or higher (e.g., about 1 millimeter, about 2millimeters, about 5 millimeters, or about 10 millimeters). At least oneof the dimensions of the profile feature (e.g., length, width, height,diameter, depending on the geometry) can be in the nanometer range(e.g., from about 10 nanometers to about 1000 nanometers), while atleast one other dimension (e.g., length, width, height, diameter,depending on the geometry) can be in the micrometer range (e.g., 5micrometers to 500 micrometers or more (e.g., about 1 to 10millimeters)). The textured surface can have a plurality of profilefeatures having at least one dimension in the nanometer range (e.g.,about 10 to 1000 nanometers) and the other in the micrometer range(e.g., 5 micrometers to 500 micrometers or more). In this context, thephrase “plurality of the profile features” is meant to mean that about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more, or about 99 percentor more of the profile features have at least one dimension in thenanometer range and at least one dimension in the micrometer range. Inparticular, at least one of the length and width of the profile featureis in the nanometer range, while the other of the length and the widthof the profile feature is in the micrometer range.

In aspects, the height of the profile features can be greater than 250nanometers. In this context, the phrase “plurality of the profilefeatures” is meant to mean that about 50 percent or more, about 60percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have at height that is greater than 250 nanometers. The heightof the profile feature can be 250 nanometers, about 300 nanometers,about 400 nanometers, or about 500 nanometers, to about 300 nanometers,about 400 nanometers, about 500 nanometers, or about 1000 nanometers ormore. For example, the range can be 250 nanometers to about 1000nanometers, about 300 nanometers to 500 nanometers, about 400 nanometersto about 1000 nanometers, and the like. One or more of the otherdimensions (e.g., length, width, diameter, or the like) can be in themicrometer to millimeter range (e.g., greater than 500 micrometers to 10millimeters). In particular, at least one of the length and width of theprofile feature is in the nanometer range (e.g., about 10 to 1000nanometers) and the other in the micrometer range (e.g., 5 micrometersto 500 micrometers or more), while the height is greater than 250nanometers.

The profile features can have a certain spatial arrangement. The spatialarrangement of the profile features may be uniform, such as spacedevenly apart or forming a pattern. The spatial arrangement can berandom. Adjacent profile features can be about 10 to 500 nanometersapart, about 100 to 1000 nanometers apart, about 1 to 100 micrometersapart or about 5 to 100 micrometers apart. Adjacent profile features canoverlap one another or be adjacent one another so little or no flatregions are positioned there between. The desired spacing can depend, atleast in part, on the size and/or shape of the profile structures andthe desired achromatic structural color effect.

The profile features can have a certain cross-sectional shape (withrespect to a plane parallel the first plane). The textured surface canhave a plurality of profile features having the same or similarcross-sectional shape. The textured surface has a plurality of profilefeatures having a mixture of different cross-sectional shapes. Thecross-sectional shapes of the profile features can include polygonal(e.g., square or triangle or rectangle cross section), circular,semi-circular, tubular, oval, random, high and low aspect ratios,overlapping profile features, and the like.

The profile feature (e.g., about 10 nanometers to 500 micrometers) caninclude an upper, flat surface. The profile feature (e.g., about 10nanometers to 500 micrometers) can include an upper, concavely curvedsurface. The concave curved surface may extend symmetrically either sideof an uppermost point. The concave curved surface may extendsymmetrically across only 50 percent of the uppermost point. The profilefeature (e.g., about 10 nanometers to 500 micrometers) can include anupper, convexly curved surface. The curved surface may extendsymmetrically either side of an uppermost point. The curved surface mayextend symmetrically across only 50 percent of the uppermost point.

The profile feature can include protrusions from the textured surface.The profile feature can include indents (hollow areas) formed in thetextured surface. The profile feature can have a smooth, curved shape(e.g., a polygonal cross-section with curved corners).

The profile features (whether protrusions or depressions) can beapproximately conical or frusto-conical (i.e. the projections or indentsmay have horizontally or diagonally flattened tops) or have anapproximately part-spherical surface (e.g., a convex or concave surfacerespectively having a substantially even radius of curvature).

The profile features may have one or more sides or edges that extend ina direction that forms an angle to the first plane of the texturedsurface. The angle between the first plane and a side or edge of theprofile feature is about 45 degrees or less, about 30 degrees or less,about 25 degrees or less, or about 20 degrees or less. The one or moresides or edges may extend in a linear or planar orientation, or may becurved so that the angle changes as a function of distance from thefirst plane. The profile features may have one or more sides thatinclude step(s) and/or flat side(s). The profile feature can have one ormore sides (or portions thereof) that can be orthogonal or perpendicularto the first plane of the textured surface, or extend at an angle ofabout 10 degrees to 89 degrees to the first plane (90 degrees beingperpendicular or orthogonal to the first plane)). The profile featurecan have a side with a stepped configuration, where portions of the sidecan be parallel to the first plane of the textured surface or have anangle of about 1 degrees to 179 degrees (0 degrees being parallel to thefirst plane)).

The textured surface can have profile features with varying shapes(e.g., the profile features can vary in shape, height, width and lengthamong the profile features) or profile features with substantiallyuniform shapes and/or dimensions. The achromatic structural colorproduced by the textured surface can be determined, at least in part, bythe shape, dimensions, spacing, and the like, of the profile features.

The profile features can be shaped so as to result in a portion of thesurface (e.g., about 25 to 50 percent or more) being about normal to theincoming light when the light is incident at the normal to the firstplane of the textured surface. The profile features can be shaped so asto result in a portion of the surface (e.g., about 25 to 50 percent ormore) being about normal to the incoming light when the light isincident at an angle of up to 45 degrees to the first plane of thetextured surface.

The spatial orientation of the profile features on the textured surfacecan be used to produce the achromatic structural color, or to effect thedegree to which the achromatic structural color shifts at differentviewing angles. The spatial orientation of the profile features on thetextured surface can be random, a semi-random pattern, or in a setpattern. A set pattern of profile features is a known set up orconfiguration of profile features in a certain area (e.g., about 50nanometers squared to about 10 millimeters squared depending upon thedimensions of the profile features (e.g., any increment between about 50nanometers and about 10 millimeters is included)). A semi-random patternof profile features is a known set up of profile features in a certainarea (e.g., about 50 nanometers squared to 10 millimeters squared) withsome deviation (e.g., 1 to 15% deviation from the set pattern), whilerandom profile features are present in the area but the pattern ofprofile features is discernable. A random spatial orientation of theprofile features in an area produces no discernable pattern in a certainarea, (e.g., about 50 nanometers squared to 10 millimeters squared).

The spatial orientation of the profile features can be periodic (e.g.,full or partial) or non-periodic. A periodic spatial orientation of theprofile features is a recurring pattern at intervals. The periodicity ofthe periodic spatial orientation of the profile features can depend uponthe dimensions of the profile features but generally are periodic fromabout 50 nanometers to 100 micrometers. For example, when the dimensionsof the profile features are submicron, the periodicity of the periodicspatial orientation of the profile features can be in the 50 to 500nanometer range or 100 to 1000 nanometer range. In another example, whenthe dimensions of the profile features are at the micron level, theperiodicity of the periodic spatial orientation of the profile featurescan be in the 10 to 500 micrometer range or 10 to 1000 micrometer range.A full periodic pattern of profile features indicates that the entirepattern exhibits periodicity, whereas partial periodicity indicates thatless than all of the pattern exhibits periodicity (e.g., about 70-99percent of the periodicity is retained). A non-periodic spatialorientation of profile features is not periodic and does not showperiodicity based on the dimensions of the profile features, inparticular, no periodicity in the 50 to 500 nanometer range or 100 to1000 nanometer range where the dimensions are of the profile featuresare submicron or no periodicity in the 10 to 500 micrometer range or 10to 1000 micrometer range where the dimensions are of the profilefeatures are in the micron range.

In an aspect, the spatial orientation of the profile features on thetextured surface can be set to reduce distortion effects, e.g., causedby the interference of one profile feature with another in regard to theachromatic structural color of the article. Since the shape, dimension,relative orientation of the profile features can vary considerablyacross the textured surface, the desired spacing and/or relativepositioning for a particular area (e.g., in the micrometer range orabout 1 to 10 square micrometers) having profile features can beappropriately determined. As discussed herein, the shape, dimension,relative orientation of the profile features affect the contours of thereflective layer(s) and/or constituent layer(s), so the dimensions(e.g., thickness), index of refraction, number of layers in the opticalelement (e.g., reflective layer(s) and constituent layer(s)) areconsidered when designing the textured side of the texture layer.

The profile features are located in nearly random positions relative toone another across a specific area of the textured surface (e.g., in themicrometer range or about 1 to 10 square micrometers to centimeter rangeor about 0.5 to 5 square centimeters, and all range increments therein),where the randomness does not defeat the purpose of producing theachromatic structural color. In other words, the randomness isconsistent with the spacing, shape, dimension, and relative orientationof the profile features, the dimensions (e.g., thickness), index ofrefraction, and number of layers (e.g., the reflective layer(s), theconstituent layer(s), and the like, with the goal to achieve theachromatic structural color or to not impart structural color uses thefeatures (e.g., the materials, number, and thickness of the layers ofthe optical element determine the achromatic structural color).

The profile features can be positioned in a set manner relative to oneanother across a specific area of the textured surface to achieve thepurpose of producing the achromatic structural color or to notcontribute to the production of the achromatic structural color. Therelative positions of the profile features do not necessarily follow apattern, but can follow a pattern consistent with the desired achromaticstructural color. As mentioned above and herein, various parametersrelated to the profile features, flat areas, and reflective layer(s)and/or the constituent layer can be used to position the profilefeatures in a set manner relative to one another.

The textured surface can include micro and/or nanoscale profile featuresthat can form gratings (e.g., a diffractive grating), photonic crystalstructure, a selective mirror structure, crystal fiber structures,deformed matrix structures, spiraled coiled structures, surface gratingstructures, and combinations thereof. The textured surface can includemicro and/or nanoscale profile features that form a grating having aperiodic or non-periodic design structure to impart the achromaticstructural color or to not contribute to the production of theachromatic structural color. The micro and/or nanoscale profile featurescan have a peak-valley pattern of profile features and/or flat areas toproduce the desired achromatic structural color. The grading can be anEchelette grating.

The profile features and the flat areas of the textured surface in theoptical element can appear as topographical undulations in each layer(e.g., reflective layer(s) and/or the constituent layer(s)). Forexample, referring to FIG. 2A, an optical element 200 includes atextured structure 220 having a plurality of profile features 222 andflat areas 224. As described herein, one or more of the profile features222 can be projections from a surface of the textured structure 220,and/or one or more of the profile features can be depressions in asurface of the textured structure 220 (not shown). One or moreconstituent layers 240 are disposed on the textured structure 220 andthen a reflective layer 230 and one or more constituent layers 245 aredisposed on the preceding layers. In some embodiments, the resultingtopography of the textured structure 220 and the one or more constituentlayers 240 and 245 and the reflective layer 230 are not identical, butrather, the one or more constituent layers 240 and 245 and thereflective layer 230 can have elevated or depressed regions 242 whichare either elevated or depressed relative to the height of the planarregions 244 and which roughly correspond to the location of the profilefeatures 222 of the textured structure 220. The one or more constituentlayers 240 and 245 and the reflective layer 230 have planar regions 244that roughly correspond to the location of the flat areas 224 of thetextured structure 220. Due to the presence of the elevated or depressedregions 242 and the planar regions 244, the resultant overall topographyof the one or more constituent layers 240 and 245 and the reflectivelayer 230 can be that of an undulating or wave-like structure. Thedimension, shape, and spacing of the profile features along with thenumber of layers of the constituent layer, the reflective layer, thethickness of each of the layers, refractive index of each layer, and thetype of material, can be used to produce an optical element whichresults in a particular achromatic structural color or to not contributeto the production of the achromatic structural color.

While the textured surface can produce the achromatic structural colorin some embodiments, or can affect the degree to which the achromaticstructural color shifts at different viewing angles, in otherembodiments, a “textured surface” or surface with texture may notproduce the achromatic structural color, or may not affect the degree towhich the achromatic structural color shifts at different viewingangles. The achromatic structural color can be produced by the design ofthe optical element with or without the textured surface. As a result,the optical element can include the textured surface having profileelements of dimensions in the nanometer to millimeter range, but theachromatic structural color or the shifting of the achromatic structuralcolor is not attributable to the presence or absence of the texturedsurface. In other words, the optical element imparts the same achromaticstructural color whether or not the textured surface is present Thedesign of the textured surface can be configured to not affect theachromatic structural color imparted by the optical element, or notaffect the shifting of the achromatic structural color imparted by theoptical element. The shape of the profile features, dimensions of theshapes, the spatial orientation of the profile features relative to oneanother, and the like can be selected so that the textured surface doesnot affect the achromatic structural color attributable to the opticalelement.

The achromatic structural color imparted by a first optical element anda second optical element, where the only difference between the firstand second optical element is that the first optical element includes atextured surface, can be compared. A color measurement can be performedfor each of the first and second optical element at the same relativeangle, where a comparison of the color measurements can determine what,if any, change is correlated to the presence of the textured surface.For example, at a first observation angle the achromatic structuralcolor is a first achromatic structural color for the first opticalelement and at the first observation angle the achromatic structuralcolor is a second achromatic structural color for the second opticalelement. Since the structural color is achromatic structural color a*and b* do not change (or change very little (e.g., less than 1 percent,less than 2 percent, less than 3 percent, or less than 5 percent)),while L* can change. As a result, the first color measurement can beobtained and has coordinate L₁* (while a₁* and b₁* can be measured, theydo not change since the structural color is achromatic, which results intheir value being zero in the ΔE*_(ab) equation), while a second colormeasurement can be obtained and has coordinate L₂* (while a₂* and b₂*can be measured, they do not change since the structural color isachromatic, which results in their value being zero in the ΔE*_(ab)equation), according to the CIE 1976 color space under a givenillumination condition.

When ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 2.2 or is less than or equalto about 3, the first achromatic structural color associated with thefirst color measurement and the second achromatic structural colorassociated with the second color measurement are the same or notperceptibly different to an average observer (e.g., the textured surfacedoes not cause or change the achromatic structural color by more than 20percent, 10 percent, or 5 percent). When ΔE*_(ab) between the firstcolor measurement and the second color measurement is greater than 3 oroptionally greater than about 4 or 5, the first structural colorassociated with the first color measurement and the second structuralcolor associated with the second color measurement are different orperceptibly different to an average observer (e.g., the textured surfacedoes change the achromatic structural color by more than 20 percent, 10percent, or 5 percent). For example, the achromatic structural color canchange from white to neutral gray, black to neutral gray, or changealong the neutral gray spectrum.

In another approach, when the percent difference between L₁* and L₂* isless than 20 percent, the first achromatic structural color associatedwith the first color measurement and the second achromatic structuralcolor associated with the second color measurement are the same or notperceptibly different to an average observer (e.g., the textured surfacedoes not cause or change the achromatic structural color by less than 20percent, 10 percent, or 5 percent). When the percent difference betweenone or more of values L₁* and L₂* is greater than 20 percent, the firstachromatic structural color associated with the first color measurementand the second achromatic structural color associated with the secondcolor measurement are different or perceptibly different to an averageobserver (e.g., the textured surface does change the achromaticstructural color by more than 20 percent, 10 percent, or 5 percent).

In another case, the achromatic structural color imparted by a firstoptical element and a second optical element, where the only differentbetween the first and second optical element is that the first opticalelement includes a textured surface, can be compared at different anglesof incident light upon the optical element or different observationangles. A color measurement can be performed for each of the first andsecond optical element at different angles (e.g., angle between −15degrees and 180 degrees between −15 degrees and +60 degrees and whichare at least 15 degrees apart from each other), where a comparison ofthe color measurements can determine what, if any, change is correlatedto the presence of the textured surface a different angles. For example,at a first observation angle the achromatic structural color is a firstachromatic structural color for the first optical element and at secondobservation angle the achromatic structural color is a second achromaticstructural color for the second optical element. The first colormeasurement can be obtained and has coordinate L₁*, while a second colormeasurement can be obtained and has coordinate L₂* can be obtained,according to the CIE 1976 color space under a given illuminationcondition.

When ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 2.2 or is less than or equalto about 3, the first achromatic structural color associated with thefirst color measurement and the second achromatic structural colorassociated with the second color measurement are the same or notperceptibly different to an average observer (e.g., the textured surfacedoes not cause or change the achromatic structural color based ondifferent angles of incident light upon the optical elements ordifferent observation angles). When ΔE*_(ab) between the first colormeasurement and the second color measurement is greater than 3 oroptionally greater than about 4 or 5, the first achromatic structuralcolor associated with the first color measurement and the secondachromatic structural color associated with the second color measurementare different or perceptibly different to an average observer (e.g., thetextured surface does change the structural color at different angles ofincident light upon the optical elements or different observationangles).

In another approach, when the percent difference between L₁* and L₂* isless than 20 percent, the first achromatic structural color associatedwith the first color measurement and the second achromatic structuralcolor associated with the second color measurement are the same or notperceptibly different to an average observer (e.g., the textured surfacedoes not cause or change the achromatic structural color by more than 20percent, 10 percent, or 5 percent at different angles of incident lightupon the optical element or different observation angles). When thepercent difference between one or more of values L₁* and L₂* is greaterthan 20 percent, the first achromatic structural color associated withthe first color measurement and the second achromatic structural colorassociated with the second color measurement are different orperceptibly different to an average observer (e.g., the textured surfacedoes change the achromatic structural color by more than 20 percent, 10percent, or 5 percent at different angles of incident light upon theoptical element or different observation angles).

In another embodiment, the achromatic structural color can be impartedby the optical element without the textured surface. The surface of thelayers of the optical element are substantially flat (or substantiallythree dimensional flat planar surface) or flat (or three dimensionalflat planar surface) at the microscale (e.g., about 1 to 500micrometers) and/or nanoscale (e.g., about 50 to 500 nanometers). Inregard to substantially flat or substantially planar the surface caninclude some minor topographical features (e.g., nanoscale and/ormicroscale) such as those that might be caused due to unintentionalimperfections, slight undulations that are unintentional, othertopographical features (e.g., extensions above the plane of the layer ordepressions below or into the plane of the layer) caused by theequipment and/or process used and the like that are unintentionallyintroduced. The topographical features do not resemble profile featuresof the textured surface. In addition, the substantially flat (orsubstantially three dimensional flat planar surface) or flat (or threedimensional flat planar surface) may include curvature as the dimensionsof the optical element increase, for example about 500 micrometers ormore, about 10 millimeter or more, about 10 centimeters or more,depending upon the dimensions of the optical element, as long as thesurface is flat or substantially flat and the surface only includes someminor topographical features. In an aspect, the profile features of thetextured surface described herein are excluded from is referred to assubstantially flat (or substantially three dimensional flat planarsurface) or flat (or three dimensional flat planar surface). The area ofthe substantially three dimensional flat planar surface or a threedimensional flat planar surface can be about 1 centimeter squared toabout 5 centimeter squared, about 1 centimeter squared to about 10centimeter squared, about 1 centimeter squared to about 15 centimetersquared, about 1 centimeter squared to about 20 centimeter squared,about 3 centimeter squared to about 10 centimeter squared, about 5centimeter squared to about 20 centimeter squared, or about 5 centimetersquared to about 50 centimeter squared.

FIG. 2B is a cross-section illustration of a substantially flat (orsubstantially three dimensional flat planar surface) or flat (or threedimensional flat planar surface) optical element 300. The opticalelement 300 includes one or more constituent layers 340 are disposed onthe flat or three dimensional flat planar surface structure 320 and thena reflective layer 330 and one or more constituent layers 345 aredisposed on the preceding layers. The material that makes up theconstituent layers and the reflective layer, number of layers of theconstituent layer, the reflective layer, the thickness of each of thelayers, refractive index of each layer, and the like, can produce anoptical element which results in a particular achromatic structuralcolor.

As described herein, a layer of the optical element further includes atextured surface. The optical element is on the textured surface andlightness (e.g., L* of CIE 1976 color space or CIELAB) (optionally a hueand/or a chroma), is altered by the textured surface, as determined bycomparing the optical element comprising the textured surface of asubstantially identical optical element (e.g., material used, thickness,and the like) which is free of the textured surface.

A layer of the optical element further includes a textured surface andthe optical element is on the textured surface. The textured surfacereduces or eliminates shift of the achromatic structural color as aviewing angle is varied from a first viewing angle to a second viewingangle, as compared to a substantially identical optical element (e.g.,material used, thickness, and the like) which is free of the texturedsurface.

A layer of the optical element further includes a textured surface andthe optical element is on the textured surface. Lightness (e.g., L* ofCIE 1976 color space or CIELAB) (optionally a hue and/or a chroma), isunaffected by or substantially unaffected (e.g., affected by about 1% orless, about 0.1 to 2%, about 0.1 to 3%, about 0.1 to 5%, or about 0.1 to7.5%) by the textured surface, as determined by comparing the opticalelement comprising the textured surface to a substantially identicaloptical element (e.g., material used, thickness, and the like) which isfree of the textured surface.

A layer of the optical element further includes a textured surface andthe optical element is on the textured surface. A shift of theachromatic structural color is unaltered by or substantially the same asa viewing angle is varied from a first viewing angle to a second viewingangle, as compared to a substantially identical optical element (e.g.,material used, thickness, and the like) which is free of the texturedsurface.

The surface of the article is a textured surface and the optical elementis on the textured surface. Lightness (e.g., L* of CIE 1976 color spaceor CIELAB) (optionally a hue and/or a chroma) is altered by the texturedsurface, as determined by comparing the optical element comprising thetextured surface of a substantially identical optical element (e.g.,material used, thickness, and the like) on a surface of a substantiallyidentical article (e.g., material used, design, and the like) which isfree of the textured surface.

The surface of the article is a textured surface and the optical elementis on the textured surface. The textured surface reduces (e.g., by about80% to 99%, about 85 to 99%, about 90 to 99%, about 95 to 99%, or about98 to 99%) or eliminates shift of the achromatic structural color as aviewing angle is varied from a first viewing angle to a second viewingangle, as compared to a substantially identical optical element (e.g.,material used, thickness, and the like) on a surface of a substantiallyidentical article (e.g., material used, design, and the like) which isfree of the texture.

The surface of the article is a textured surface and the optical elementis on the textured surface. Lightness (e.g., L* of CIE 1976 color spaceor CIELAB) (optionally a hue and/or a chroma) is unaffected by orsubstantially unaffected (e.g., affected by about 1% or less, about 0.1to 2%, about 0.1 to 3%, about 0.1 to 5%, or about 0.1 to 7.5%) by thetextured surface, as determined by comparing the optical elementcomprising the textured surface to a substantially identical opticalelement (e.g., material used, thickness, and the like) on a surface of asubstantially identical article (e.g., material used, design, and thelike) which is free of the textured surface.

The surface of the article is a textured surface and the optical elementis on the textured surface. The shift of the achromatic structural coloris unaltered by or substantially the same (e.g., by about 80% to 99%,about 85 to 99%, about 90 to 99%, about 95 to 99%, or about 98 to 99%the same) as a viewing angle is varied from a first viewing angle to asecond viewing angle, as compared to a substantially identical opticalelement (e.g., material used, thickness, and the like) on a surface of asubstantially identical article (e.g., material used, design, and thelike) which is free of the textured surface.

The textured surface includes a plurality of profile features and flatplanar areas, where the profile features extend above the flat areas ofthe textured surface. The dimensions of the profile features, a shape ofthe profile features, a spacing among the plurality of the profilefeatures, or any combination thereof, in combination with the opticalelement, affect lightness (e.g., L* of CIE 1976 color space or CIELAB)(optionally a hue and/or a chroma) or a shift of the achromaticstructural color as a viewing angle is varied from a first viewing angleto a second viewing angle, or any combination thereof.

Lightness (e.g., L* of CIE 1976 color space or CIELAB) (optionally a hueand/or a chroma) or a shift of the structural color as a viewing angleis varied from a first viewing angle to a second viewing angle, or anycombination thereof, are unaffected or substantially unaffected (e.g.,affected by about 1% or less, about 0.1 to 2%, about 0.1 to 3%, about0.1 to 5%, or about 0.1 to 7.5%) by dimensions of the profile features,a shape of the profile features, a spacing among the plurality of theprofile features, or any combination thereof, of the textured surface.

The profile features of the textured surface are in random positionsrelative to one another within a specific area. The spacing between theprofile features, in combination with the optical element, affectslightness (e.g., L* of CIE 1976 color space or CIELAB) (optionally a hueand/or a chroma) or a shift of the structural color as a viewing angleis varied from a first viewing angle to a second viewing angle, or anycombination thereof.

Lightness (e.g., L* of CIE 1976 color space or CIELAB) (optionally a hueand/or a chroma) or a shift of the achromatic structural color as aviewing angle is varied from a first viewing angle to a second viewingangle, or any combination thereof, is unaffected by, or substantiallyunaffected (e.g., affected by about 1% or less, about 0.1 to 2%, about0.1 to 3%, about 0.1 to 5%, or about 0.1 to 7.5%) by, spacing betweenthe profile features in combination with the optical element.

The profile features and the flat areas result in at least one layer ofthe optical element having an undulating topography across the texturedsurface and where there is a planar region between neighboring profilefeatures that is planar with the flat planar areas of the texturedsurface.

The dimensions of the planar region relative to the profile featuresaffect lightness (e.g., L* of CIE 1976 color space or CIELAB)(optionally a hue and/or a chroma) or a shift of the structural color asa viewing angle is varied from a first viewing angle to a second viewingangle, or any combination thereof.

Lightness (e.g., L* of CIE 1976 color space or CIELAB) (optionally a hueand/or a chroma) or a shift of the achromatic structural color as aviewing angle is varied from a first viewing angle to a second viewingangle, or any combination thereof, is unaffected by or substantiallyunaffected (e.g., affected by about 1% or less, about 0.1 to 2%, about0.1 to 3%, about 0.1 to 5%, or about 0.1 to 7.5%) by dimensions of theplanar region relative to the profile features.

The profile features and the flat areas result in each layer of theoptical element having an undulating topography across the texturedsurface. The undulating topography of the optical element affectslightness (e.g., L* of CIE 1976 color space or CIELAB) (optionally a hueand/or a chroma) or a shift of the achromatic structural color as aviewing angle is varied from a first viewing angle to a second viewingangle, or any combination thereof. Lightness (e.g., L* of CIE 1976 colorspace or CIELAB) (optionally a hue and/or a chroma) or a shift of theachromatic structural color as a viewing angle is varied from a firstviewing angle to a second viewing angle, or any combination thereof, isunaffected by or substantially unaffected (e.g., affected by about 1% orless, about 0.1 to 2%, about 0.1 to 3%, about 0.1 to 5%, or about 0.1 to7.5%) by the undulating topography of the optical element.

Additional details are provided regarding the polymeric materialsreferenced herein for example, the polymers described in reference tothe article, components of the article, structures, layers, films,bladders, foams, primer layer, coating, and like the. The polymericmaterial includes at least one polymer. The polymer can be a thermosetpolymer or a thermoplastic polymer. The polymer can be an elastomericpolymer, including an elastomeric thermoset polymer or an elastomericthermoplastic polymer. The polymer can be selected from: polyurethanes(including elastomeric polyurethanes, thermoplastic polyurethanes(TPUs), and elastomeric TPUs), polyesters, polyethers, polyamides, vinylpolymers (e.g., copolymers of vinyl alcohol, vinyl esters, ethylene,acrylates, methacrylates, styrene, and so on), polyacrylonitriles,polyphenylene ethers, polycarbonates, polyureas, polystyrenes,co-polymers thereof (including polyester-polyurethanes,polyether-polyurethanes, polycarbonate-polyurethanes, polyether blockpolyamides (PEBAs), and styrene block copolymers), and any combinationthereof, as described herein. The polymer can include one or morepolymers selected from the group consisting of polyesters, polyethers,polyamides, polyurethanes, polyolefins copolymers of each, andcombinations thereof.

The term “polymer” refers to a chemical compound formed of a pluralityof repeating structural units referred to as monomers. Polymers oftenare formed by a polymerization reaction in which the plurality ofstructural units become covalently bonded together. When the monomerunits forming the polymer all have the same chemical structure, thepolymer is a homopolymer. When the polymer includes two or more monomerunits having different chemical structures, the polymer is a copolymer.One example of a type of copolymer is a terpolymer, which includes threedifferent types of monomer units. The co-polymer can include two or moredifferent monomers randomly distributed in the polymer (e.g., a randomco-polymer). Alternatively, one or more blocks containing a plurality ofa first type of monomer can be bonded to one or more blocks containing aplurality of a second type of monomer, forming a block copolymer. Asingle monomer unit can include one or more different chemicalfunctional groups.

Polymers having repeating units which include two or more types ofchemical functional groups can be referred to as having two or moresegments. For example, a polymer having repeating units of the samechemical structure can be referred to as having repeating segments.Segments are commonly described as being relatively harder or softerbased on their chemical structures, and it is common for polymers toinclude relatively harder segments and relatively softer segments bondedto each other in a single monomeric unit or in different monomericunits. When the polymer includes repeating segments, physicalinteractions or chemical bonds can be present within the segments orbetween the segments or both within and between the segments. Examplesof segments often referred to as hard segments include segmentsincluding a urethane linkage, which can be formed from reacting anisocyanate with a polyol to form a polyurethane. Examples of segmentsoften referred to as soft segments include segments including an alkoxyfunctional group, such as segments including ether or ester functionalgroups, and polyester segments. Segments can be referred to based on thename of the functional group present in the segment (e.g., a polyethersegment, a polyester segment), as well as based on the name of thechemical structure which was reacted in order to form the segment (e.g.,a polyol-derived segment, an isocyanate-derived segment). When referringto segments of a particular functional group or of a particular chemicalstructure from which the segment was derived, it is understood that thepolymer can contain up to 10 mole percent of segments of otherfunctional groups or derived from other chemical structures. Forexample, as used herein, a polyether segment is understood to include upto 10 mole percent of non-polyether segments.

As previously described, the polymer can be a thermoplastic polymer. Ingeneral, a thermoplastic polymer softens or melts when heated andreturns to a solid state when cooled. The thermoplastic polymertransitions from a solid state to a softened state when its temperatureis increased to a temperature at or above its softening temperature, anda liquid state when its temperature is increased to a temperature at orabove its melting temperature. When sufficiently cooled, thethermoplastic polymer transitions from the softened or liquid state tothe solid state. As such, the thermoplastic polymer may be softened ormelted, molded, cooled, re-softened or re-melted, re-molded, and cooledagain through multiple cycles. For amorphous thermoplastic polymers, thesolid state is understood to be the “rubbery” state above the glasstransition temperature of the polymer. The thermoplastic polymer canhave a melting temperature from about 90 degrees C. to about 190 degreesC. when determined in accordance with ASTM D3418-97 as described hereinbelow, and includes all subranges therein in increments of 1 degree. Thethermoplastic polymer can have a melting temperature from about 93degrees C. to about 99 degrees C. when determined in accordance withASTM D3418-97 as described herein below. The thermoplastic polymer canhave a melting temperature from about 112 degrees C. to about 118degrees C. when determined in accordance with ASTM D3418-97 as describedherein below.

The glass transition temperature is the temperature at which anamorphous polymer transitions from a relatively brittle “glassy” stateto a relatively more flexible “rubbery” state. The thermoplastic polymercan have a glass transition temperature from about −20 degrees C. toabout 30 degrees C. when determined in accordance with ASTM D3418-97 asdescribed herein below. The thermoplastic polymer can have a glasstransition temperature (from about −13 degree C. to about −7 degrees C.when determined in accordance with ASTM D3418-97 as described hereinbelow. The thermoplastic polymer can have a glass transition temperaturefrom about 17 degrees C. to about 23 degrees C. when determined inaccordance with ASTM D3418-97 as described herein below.

The thermoplastic polymer can have a melt flow index from about 10 toabout 30 cubic centimeters per 10 minutes (cm3/10 min) when tested inaccordance with ASTM D1238-13 as described herein below at 160 degreesC. using a weight of 2.16 kilograms (kg). The thermoplastic polymer canhave a melt flow index from about 22 cm³/10 min to about 28 cm³/10 minwhen tested in accordance with ASTM D1238-13 as described herein belowat 160 degrees C. using a weight of 2.16 kg.

The thermoplastic polymer can have a cold Ross flex test result of about120,000 to about 180,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below. Thethermoplastic polymer can have a cold Ross flex test result of about140,000 to about 160,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below.

The thermoplastic polymer can have a modulus from about 5 megaPascals(MPa) to about 100 MPa when determined on a thermoformed plaque inaccordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubberand Thermoplastic Rubbers and Thermoplastic Elastomers-Tension withmodifications described herein below. The thermoplastic polymer can havea modulus from about 20 MPa to about 80 MPa when determined on athermoformed plaque in accordance with ASTM D412-98 Standard TestMethods for Vulcanized Rubber and Thermoplastic Rubbers andThermoplastic Elastomers-Tension with modifications described hereinbelow.

The polymer can be a thermoset polymer. As used herein, a “thermosetpolymer” is understood to refer to a polymer which cannot be heated andmelted, as its melting temperature is at or above its decompositiontemperature. A “thermoset material” refers to a material which comprisesat least one thermoset polymer. The thermoset polymer and/or thermosetmaterial can be prepared from a precursor (e.g., an uncured or partiallycured polymer or material) using thermal energy and/or actinic radiation(e.g., ultraviolet radiation, visible radiation, high energy radiation,infrared radiation) to form a partially cured or fully cured polymer ormaterial which no longer remains fully thermoplastic. In some cases, thecured or partially cured polymer or material may remain thermoelasticproperties, in that it is possible to partially soften and mold thepolymer or material at elevated temperatures and/or pressures, but it isnot possible to melt the polymer or material. The curing can bepromoted, for example, with the use of high pressure and/or a catalyst.In many examples, the curing process is irreversible since it results incross-linking and/or polymerization reactions of the precursors. Theuncured or partially cured polymers or materials can be malleable orliquid prior to curing. In some cases, the uncured or partially curedpolymers or materials can be molded into their final shape, or used asadhesives. Once hardened, a thermoset polymer or material cannot bere-melted in order to be reshaped. The textured surface can be formed bypartially or fully curing an uncured precursor material to lock in thetextured surface.

Polyurethane

The polymer can be a polyurethane, such as a thermoplastic polyurethane(also referred to as “TPU”). Alternatively, the polymer can be athermoset polyurethane. Additionally, polyurethane can be an elastomericpolyurethane, including an elastomeric TPU or an elastomeric thermosetpolyurethane. The elastomeric polyurethane can include hard and softsegments. The hard segments can comprise or consist of urethane segments(e.g., isocyanate-derived segments). The soft segments can comprise orconsist of alkoxy segments (e.g., polyol-derived segments includingpolyether segments, or polyester segments, or a combination of polyethersegments and polyester segments). The polyurethane can comprise orconsist essentially of an elastomeric polyurethane having repeating hardsegments and repeating soft segments.

One or more of the polyurethanes can be produced by polymerizing one ormore isocyanates with one or more polyols to produce polymer chainshaving carbamate linkages (—N(CO)O—), where the isocyanate(s) eachpreferably include two or more isocyanate (—NCO) groups per molecule,such as 2, 3, or 4 isocyanate groups per molecule (although,mono-functional isocyanates can also be optionally included, e.g., aschain terminating units).

Additionally, the isocyanates can also be chain extended with one ormore chain extenders to bridge two or more isocyanates, increasing thelength of the hard segment.

The term “aliphatic” refers to a saturated or unsaturated organicmolecule or portion of a molecule that does not include a cyclicallyconjugated ring system having delocalized pi electrons. In comparison,the term “aromatic” refers to an organic molecule or portion of amolecule having a cyclically conjugated ring system with delocalized pielectrons, which exhibits greater stability than a hypothetical ringsystem having localized pi electrons.

Examples of suitable aliphatic diisocyanates for producing thepolyurethane polymer chains include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, and combinationsthereof.

The isocyanate-derived segments can include segments derived fromaliphatic diisocyanate. A majority of the isocyanate-derived segmentscan comprise segments derived from aliphatic diisocyanates. At least 90%of the isocyanate-derived segments are derived from aliphaticdiisocyanates. The isocyanate-derived segments can consist essentiallyof segments derived from aliphatic diisocyanates. The aliphaticdiisocyanate-derived segments can be derived substantially (e.g., about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more) from linearaliphatic diisocyanates. At least 80% of the aliphaticdiisocyanate-derived segments can be derived from aliphaticdiisocyanates that are free of side chains. The segments derived fromaliphatic diisocyanates can include linear aliphatic diisocyanateshaving from 2 to 10 carbon atoms.

Examples of suitable aromatic diisocyanates for producing thepolyurethane polymer chains include toluene diisocyanate (TDI), TDIadducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI),3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyldiisocyanate (DBDI), 4-chloro-1,3-phenylene diisocyanate, andcombinations thereof. The polymer chains can be substantially free ofaromatic groups.

The polyurethane polymer chains can be produced from diisocyanatesincluding HMDI, TDI, MDI, H12 aliphatics, and combinations thereof. Forexample, the polyurethane can comprise one or more polyurethane polymerchains produced from diisocyanates including HMDI, TDI, MDI, H12aliphatics, and combinations thereof.

Polyurethane chains which are at least partially crosslinked or whichcan be crosslinked, can be used in accordance with the presentdisclosure. It is possible to produce crosslinked or crosslinkablepolyurethane chains by reacting multi-functional isocyanates to form thepolyurethane. Examples of suitable triisocyanates for producing thepolyurethane chains include TDI, HDI, and IPDI adducts withtrimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates),polymeric MDI, and combinations thereof.

Examples of suitable chain extender polyols for producing thepolyurethane include ethylene glycol, lower oligomers of ethylene glycol(e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol),1,2-propylene glycol, 1,3-propylene glycol, lower oligomers of propyleneglycol (e.g., dipropylene glycol, tripropylene glycol, andtetrapropylene glycol), 1,4-butylene glycol, 2,3-butylene glycol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol,1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol,1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylatedaromatic compounds (e.g., bis(2-hydroxyethyl) ethers of hydroquinone andresorcinol, xylene-a,a-diols, bis(2-hydroxyethyl) ethers ofxylene-a,a-diols, and combinations thereof.

In some examples of the polyurethane, the polyurethane includes apolyester group. The polyester group can be derived from thepolyesterification of one or more dihydric alcohols (e.g., ethyleneglycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol,1,3-butanediol, 2-methylpentanediol 1,5-diethyleneglycol,1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with one or moredicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid,suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaicacid, thiodipropionic acid and citraconic acid and combinationsthereof). The polyester group also can be derived from polycarbonateprepolymers, such as poly(hexamethylene carbonate) glycol,poly(propylene carbonate) glycol, poly(tetramethylene carbonate)glycol,and poly(nonanemethylene carbonate) glycol. Suitable polyesters caninclude, for example, polyethylene adipate (PEA), poly(1,4-butyleneadipate), poly(tetramethylene adipate), poly(hexamethylene adipate),polycaprolactone, polyhexamethylene carbonate, poly(propylenecarbonate), poly(tetramethylene carbonate), poly(nonanemethylenecarbonate), and combinations thereof.

The polyurethane can include a polyether (e.g., a polyethylene oxide(PEO) group, a polyethylene glycol (PEG) group), a polyvinylpyrrolidonegroup, a polyacrylic acid group, or combinations thereof.

Optionally, the polyurethane can include an at least partiallycrosslinked polymeric network that includes polymer chains that arederivatives of polyurethane. The level of crosslinking can be such thatthe polyurethane retains thermoplastic properties (i.e., the crosslinkedthermoplastic polyurethane can be melted and re-solidified under theprocessing conditions described herein). The crosslinked polyurethanecan be a thermoset polymer. This crosslinked polymeric network can beproduced by polymerizing one or more isocyanates with one or morepolyamino compounds, polysulfhydryl compounds, or combinations thereof.

The polyurethane chain can be physically crosslinked to anotherpolyurethane chain through e.g., nonpolar or polar interactions betweenthe urethane or carbamate groups of the polymers (the hard segments

The polyurethane can be a thermoplastic polyurethane composed of MDI,PTMO, and 1,4-butylene glycol, as described in U.S. Pat. No. 4,523,005.Commercially available polyurethanes suitable for the present useinclude, but are not limited to those under the tradename “SANCURE”(e.g., the “SANCURE” series of polymer such as “SANCURE” 20025F) or“TECOPHILIC” (e.g., TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60)(Lubrizol, Countryside, Ill., USA), “PELLETHANE” 2355-85ATP and2355-95AE (Dow Chemical Company of Midland, Mich., USA.), “ESTANE”(e.g., ALR G 500, or 58213; Lubrizol, Countryside, Ill., USA).

Polyamides

The polymer can comprise a polyamide, such as a thermoplastic polyamide,or a thermoset polyamide. The polyamide can be an elastomeric polyamide,including an elastomeric thermoplastic polyamide or an elastomericthermoset polyamide. The polyamide can be a polyamide homopolymer havingrepeating polyamide segments of the same chemical structure.Alternatively, the polyamide can comprise a number of polyamide segmentshaving different polyamide chemical structures (e.g., polyamide 6segments, polyamide 11 segments, polyamide 12 segments, polyamide 66segments, etc.). The polyamide segments having different chemicalstructure can be arranged randomly, or can be arranged as repeatingblocks.

The polyamide can be a co-polyamide (i.e., a co-polymer includingpolyamide segments and non-polyamide segments). The polyamide segmentsof the co-polyamide can comprise or consist of polyamide 6 segments,polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, orany combination thereof. The polyamide segments of the co-polyamide canbe arranged randomly, or can be arranged as repeating segments. Thepolyamide segments can comprise or consist of polyamide 6 segments, orpolyamide 12 segments, or both polyamide 6 segment and polyamide 12segments. In the example where the polyamide segments of theco-polyamide include of polyamide 6 segments and polyamide 12 segments,the segments can be arranged randomly. The non-polyamide segments of theco-polyamide can comprise or consist of polyether segments, polyestersegments, or both polyether segments and polyester segments. Theco-polyamide can be a block co-polyamide, or can be a randomco-polyamide. The copolyamide can be formed from the polycondensation ofa polyamide oligomer or prepolymer with a second oligomer prepolymer toform a copolyamide (i.e., a co-polymer including polyamide segments.Optionally, the second prepolymer can be a hydrophilic prepolymer.

The polyamide can be a polyamide-containing block co-polymer. Forexample, the block co-polymer can have repeating hard segments, andrepeating soft segments. The hard segments can comprise polyamidesegments, and the soft segments can comprise non-polyamide segments. Thepolyamide-containing block co-polymer can be an elastomeric co-polyamidecomprising or consisting of polyamide-containing block co-polymershaving repeating hard segments and repeating soft segments. In blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within thesegments or between the segments or both within and between thesegments.

The polyamide itself, or the polyamide segment of thepolyamide-containing block co-polymer can be derived from thecondensation of polyamide prepolymers, such as lactams, amino acids,and/or diamino compounds with dicarboxylic acids, or activated formsthereof. The resulting polyamide segments include amide linkages(—(CO)NH—). The term “amino acid” refers to a molecule having at leastone amino group and at least one carboxyl group. Each polyamide segmentof the polyamide can be the same or different.

The polyamide or the polyamide segment of the polyamide-containing blockco-polymer can be derived from the polycondensation of lactams and/oramino acids.

Optionally, in order to increase the relative degree of hydrophilicityof the polyamide-containing block co-polymer, the polyamide can includea polyamide-polyether block copolymer segment.

The polyamide can comprise or consist essentially of apoly(ether-block-amide). The poly(ether-block-amide) can be formed fromthe polycondensation of a carboxylic acid terminated polyamideprepolymer and a hydroxyl terminated polyether prepolymer to form apoly(ether-block-amide).

Exemplary commercially available copolymers include, but are not limitedto, those available under the tradenames of “VESTAMID” (EvonikIndustries, Essen, Germany); “PLATAMID” (Arkema, Colombes, France),e.g., product code H2694; “PEBAX” (Arkema), e.g., product code “PEBAXMH1657” and “PEBAX MV1074”; “PEBAX RNEW” (Arkema); “GRILAMID”(EMS-Chemie AG, Domat-Ems, Switzerland), or also to other similarmaterials produced by various other suppliers.

The polyamide can be physically crosslinked through, e.g., nonpolar orpolar interactions between the polyamide groups of the polymers. Inexamples where the polyamide is a copolyamide, the copolyamide can bephysically crosslinked through interactions between the polyamidegroups, and optionally by interactions between the copolymer groups.When the co-polyamide is physically crosslinked through interactionsbetween the polyamide groups, the polyamide segments can form theportion of the polymer referred to as the hard segment, and copolymersegments can form the portion of the polymer referred to as the softsegment. For example, when the copolyamide is a poly(ether-block-amide),the polyamide segments form the hard segments of the polymer, andpolyether segments form the soft segments of the polymer. Therefore, insome examples, the polymer can include a physically crosslinkedpolymeric network having one or more polymer chains with amide linkages.

The polyamide segment of the co-polyamide can include polyamide-11 orpolyamide-12 and the polyether segment can be a segment selected fromthe group consisting of polyethylene oxide, polypropylene oxide, andpolytetramethylene oxide segments, and combinations thereof.

The polyamide can be partially or fully covalently crosslinked, aspreviously described herein. In some cases, the degree of crosslinkingpresent in the polyamide is such that, when it is thermally processed,e.g., in the form of a yarn or fiber to form the articles of the presentdisclosure, the partially covalently crosslinked thermoplastic polyamideretains sufficient thermoplastic character that the partially covalentlycrosslinked thermoplastic polyamide is melted during the processing andre-solidifies. In other cases, the crosslinked polyamide is a thermosetpolymer.

Polyesters

The polymers can comprise a polyester. The polyester can comprise athermoplastic polyester, or a thermoset polyester. Additionally, thepolyester can be an elastomeric polyester, including a thermoplasticpolyester or a thermoset elastomeric polyester. The polyester can beformed by reaction of one or more carboxylic acids, or its ester-formingderivatives, with one or more bivalent or multivalent aliphatic,alicyclic, aromatic or araliphatic alcohols or a bisphenol. Thepolyester can be a polyester homopolymer having repeating polyestersegments of the same chemical structure. Alternatively, the polyestercan comprise a number of polyester segments having different polyesterchemical structures (e.g., polyglycolic acid segments, polylactic acidsegments, polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, etc.). The polyester segments havingdifferent chemical structure can be arranged randomly, or can bearranged as repeating blocks.

Exemplary carboxylic acids that can be used to prepare a polyesterinclude, but are not limited to, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decanedicarboxylic acid, undecane dicarboxylic acid, terephthalic acid,isophthalic acid, alkyl-substituted or halogenated terephthalic acid,alkyl-substituted or halogenated isophthalic acid, nitro-terephthalicacid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl thioetherdicarboxylic acid, 4,4′-diphenyl sulfone-dicarboxylic acid,4,4′-diphenyl alkylenedicarboxylic acid, naphthalene-2,6-dicarboxylicacid, cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylicacid. Exemplary diols or phenols suitable for the preparation of thepolyester include, but are not limited to, ethylene glycol, diethyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol,1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol,2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol,1,4-cyclohexane dimethanol, and bis-phenol A.

The polyester can be a polybutylene terephthalate (PBT), apolytrimethylene terephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), a liquid crystal polyester, or a blendor mixture of two or more of the foregoing.

The polyester can be a co-polyester (i.e., a co-polymer includingpolyester segments and non-polyester segments). The co-polyester can bean aliphatic co-polyester (i.e., a co-polyester in which both thepolyester segments and the non-polyester segments are aliphatic).Alternatively, the co-polyester can include aromatic segments. Thepolyester segments of the co-polyester can comprise or consistessentially of polyglycolic acid segments, polylactic acid segments,polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, or any combination thereof. The polyestersegments of the co-polyester can be arranged randomly, or can bearranged as repeating blocks.

For example, the polyester can be a block co-polyester having repeatingblocks of polymeric units of the same chemical structure which arerelatively harder (hard segments), and repeating blocks of the samechemical structure which are relatively softer (soft segments). In blockco-polyesters, including block co-polyesters having repeating hardsegments and soft segments, physical crosslinks can be present withinthe blocks or between the blocks or both within and between the blocks.The polymer can comprise or consist essentially of an elastomericco-polyester having repeating blocks of hard segments and repeatingblocks of soft segments.

The non-polyester segments of the co-polyester can comprise or consistessentially of polyether segments, polyamide segments, or both polyethersegments and polyamide segments. The co-polyester can be a blockco-polyester, or can be a random co-polyester. The co-polyester can beformed from the polycondensation of a polyester oligomer or prepolymerwith a second oligomer prepolymer to form a block copolyester.Optionally, the second prepolymer can be a hydrophilic prepolymer. Forexample, the co-polyester can be formed from the polycondensation ofterephthalic acid or naphthalene dicarboxylic acid with ethylene glycol,1,4-butanediol, or 1,3-propanediol. Examples of co-polyesters includepolyethylene adipate, polybutylene succinate,poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate,polybutylene terephthalate, polytrimethylene terephthalate, polyethylenenapthalate, and combinations thereof. The co-polyamide can comprise orconsist of polyethylene terephthalate.

The polyester can be a block copolymer comprising segments of one ormore of polybutylene terephthalate (PBT), a polytrimethyleneterephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), and a liquid crystal polyester. Forexample, a suitable polyester that is a block copolymer can be a PET/PEIcopolymer, a polybutylene terephthalate/tetraethylene glycol copolymer,a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, ora blend or mixture of any of the foregoing.

The disclosed polyesters can be prepared by a variety ofpolycondensation methods known to the skilled artisan, such as a solventpolymerization or a melt polymerization process.

Polyolefins

The polymers can comprise or consist essentially of a polyolefin. Thepolyolefin can be a thermoplastic polyolefin or a thermoset polyolefin.Additionally, the polyolefin can be an elastomeric polyolefin, includinga thermoplastic elastomeric polyolefin or a thermoset elastomericpolyolefin. Exemplary polyolefins can include polyethylene,polypropylene, and olefin elastomers (e.g.,metallocene-catalyzed blockcopolymers of ethylene and α-olefins having 4 to about 8 carbon atoms).The polyolefin can be a polymer comprising a polyethylene, anethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), apolybutene, a polyisobutylene, a poly-4-methylpent-1-ene, apolyisoprene, a polybutadiene, a ethylene-methacrylic acid copolymer,and an olefin elastomer such as a dynamically cross-linked polymerobtained from polypropylene (PP) and an ethylene-propylene rubber(EPDM), and blends or mixtures of the foregoing. Further exemplarypolyolefins include polymers of cycloolefins such as cyclopentene ornorbornene.

It is to be understood that polyethylene, which optionally can becrosslinked, is inclusive a variety of polyethylenes, including lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE), medium density polyethylene (MDPE), high densitypolyethylene (HDPE), high density and high molecular weight polyethylene(HDPE-HMW), high density and ultrahigh molecular weight polyethylene(HDPE-UHMW), and blends or mixtures of any the foregoing polyethylenes.A polyethylene can also be a polyethylene copolymer derived frommonomers of monolefins and diolefins copolymerized with a vinyl, acrylicacid, methacrylic acid, ethyl acrylate, vinyl alcohol, and/or vinylacetate. Polyolefin copolymers comprising vinyl acetate-derived unitscan be a high vinyl acetate content copolymer, e.g., greater than about50 weight percent vinyl acetate-derived composition.

The polyolefin can be formed through free radical, cationic, and/oranionic polymerization by methods well known to those skilled in the art(e.g., using a peroxide initiator, heat, and/or light).

Suitable polyolefins can be prepared by polymerization of monomers ofmonolefins and diolefins as described herein. Exemplary monomers thatcan be used to prepare the polyolefin include, but are not limited to,ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixturesthereof.

Suitable ethylene-α-olefin copolymers can be obtained bycopolymerization of ethylene with an α-olefin such as propylene,butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like havingcarbon numbers of 3 to 12.

The polyolefin can be a mixture of polyolefins, such as a mixture of twoor more polyolefins disclosed herein above. For example, a suitablemixture of polyolefins can be a mixture of polypropylene withpolyisobutylene, polypropylene with polyethylene (for example PP/HDPE,PP/LDPE) or mixtures of different types of polyethylene (for exampleLDPE/HDPE).

The polyolefin can be a copolymer of suitable monolefin monomers or acopolymer of a suitable monolefin monomer and a vinyl monomer. Exemplarypolyolefin copolymers include ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

The polyolefin can be a polypropylene homopolymer, a polypropylenecopolymers, a polypropylene random copolymer, a polypropylene blockcopolymer, a polyethylene homopolymer, a polyethylene random copolymer,a polyethylene block copolymer, a low density polyethylene (LDPE), alinear low density polyethylene (LLDPE), a medium density polyethylene,a high density polyethylene (HDPE), or blends or mixtures of one or moreof the preceding polymers.

The polyolefin can be a polypropylene. The term “polypropylene,” as usedherein, is intended to encompass any polymeric composition comprisingpropylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as ethylene, butylene, and the like). Such a term also encompassesany different configuration and arrangement of the constituent monomers(such as atactic, syndiotactic, isotactic, and the like). Thus, the termas applied to fibers is intended to encompass actual long strands,tapes, threads, and the like, of drawn polymer. The polypropylene can beof any standard melt flow (by testing); however, standard fiber gradepolypropylene resins possess ranges of Melt Flow Indices between about 1and 1000.

The polyolefin can be a polyethylene. The term “polyethylene,” as usedherein, is intended to encompass any polymeric composition comprisingethylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as propylene, butylene, and the like). Such a term alsoencompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolyethylene can be of any standard melt flow (by testing); however,standard fiber grade polyethylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

The thermoplastic and/or thermosetting material can further comprise oneor more processing aids. The processing aid can be a non-polymericmaterial. These processing aids can be independently selected from thegroup including, but not limited to, curing agents, initiators,plasticizers, mold release agents, lubricants, antioxidants, flameretardants, dyes, pigments, reinforcing and non-reinforcing fillers,fiber reinforcements, and light stabilizers.

In articles that include a textile, the optical element can be disposedonto the textile. The textile or at least an outer layer of the textilecan includes a thermoplastic material that the optical element candisposed onto. The textile can be a nonwoven textile, a syntheticleather, a knit textile, or a woven textile. The textile can comprise afirst fiber or a first yarn, where the first fiber or the first yarn caninclude at least an outer layer comprising the first thermoplasticmaterial. A region of the first or second side of the structure ontowhich the optical element is disposed can include the first fiber or thefirst yarn in a non-filamentous conformation. The optical element can bedisposed onto the textile or the textile can be processed so that theoptical element can be disposed onto the textile. The textured surfacecan be made of or formed from the textile surface. The optical elementcan be disposed onto the primer layer. The textile surface can be usedto form the textured surface, and either before or after this, theoptical element can be applied to the textile.

A “textile” may be defined as any material manufactured from fibers,filaments, or yarns characterized by flexibility, fineness, and a highratio of length to thickness. Textiles generally fall into twocategories. The first category includes textiles produced directly fromwebs of filaments or fibers by randomly interlocking to constructnon-woven fabrics and felts. The second category includes textilesformed through a mechanical manipulation of yarn, thereby producing awoven fabric, a knitted fabric, a braided fabric, a crocheted fabric,and the like.

The terms “filament,” “fiber,” or “fibers” as used herein refer tomaterials that are in the form of discrete elongated pieces that aresignificantly longer than they are wide. The fiber can include natural,manmade or synthetic fibers. The fibers may be produced by conventionaltechniques, such as extrusion, electrospinning, interfacialpolymerization, pulling, and the like. The fibers can include carbonfibers, boron fibers, silicon carbide fibers, titania fibers, aluminafibers, quartz fibers, glass fibers, such as E, A, C, ECR, R, S, D, andNE glasses and quartz, or the like. The fibers can be fibers formedusing polymeric materials comprising polymers capable of forming fiberssuch as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylenesulfide), polyesters, polyolefins (e.g., polyethylene, polypropylene),aromatic polyamides (e.g., an aramid polymer such as para-aramid fibersand meta-aramid fibers), aromatic polyimides, polybenzimidazoles,polyetherimides, polytetrafluoroethylene, acrylic, modacrylic,poly(vinyl alcohol), polyamides, polyurethanes, and copolymers such aspolyether-polyurea copolymers, polyester-polyurethanes, polyether blockamide copolymers, or the like. The fibers can be natural fibers (e.g.,silk, wool, cashmere, vicuna, cotton, flax, hemp, jute, sisal). Thefibers can be man-made fibers from regenerated natural polymers, such asrayon, lyocell, acetate, triacetate, rubber, and poly(lactic acid).

The fibers can have an indefinite length. For example, man-made andsynthetic fibers are generally extruded in substantially continuousstrands. Alternatively, the fibers can be staple fibers, such as, forexample, cotton fibers or extruded synthetic polymer fibers can be cutto form staple fibers of relatively uniform length. The staple fiber canhave a have a length of about 1 millimeter to 100 centimeters or more aswell as any increment therein (e.g., 1 millimeter increments).

The fiber can have any of a variety of cross-sectional shapes. Naturalfibers can have a natural cross-section, or can have a modifiedcross-sectional shape (e.g., with processes such as mercerization).Man-made or synthetic fibers can be extruded to provide a strand havinga predetermined cross-sectional shape. The cross-sectional shape of afiber can affect its properties, such as its softness, luster, andwicking ability. The fibers can have round or essentially round crosssections. Alternatively, the fibers can have non-round cross sections,such as flat, oval, octagonal, rectangular, wedge-shaped, triangular,dog-bone, multi-lobal, multi-channel, hollow, core-shell, or othershapes.

The fiber can be processed. For example, the properties of fibers can beaffected, at least in part, by processes such as drawing (stretching)the fibers, annealing (hardening) the fibers, and/or crimping ortexturizing the fibers.

In some cases a fiber can be a multi-component fiber, such as onecomprising two or more co-extruded polymeric materials. The two or moreco-extruded polymeric materials can be extruded in a core-sheath,islands-in-the-sea, segmented-pie, striped, or side-by-sideconfiguration. A multi-component fiber can be processed in order to forma plurality of smaller fibers (e.g., microfibers) from a single fiber,for example, by remove a sacrificial material.

The fiber can be a carbon fiber such as TARIFYL produced by FormosaPlastics Corp. of Kaohsiung City, Taiwan, (e.g., 12,000, 24,000, and48,000 fiber tows, specifically fiber types TC-35 and TC-35R), carbonfiber produced by SGL Group of Wiesbaden, Germany (e.g., 50,000 fibertow), carbon fiber produced by Hyosung of Seoul, South Korea, carbonfiber produced by Toho Tenax of Tokyo, Japan, fiberglass produced byJushi Group Co., LTD of Zhejiang, China (e.g., E6, 318, silane-basedsizing, filament diameters 14, 15, 17, 21,and 24 micrometers), andpolyester fibers produced by Amann Group of Bonningheim, Germany (e.g.,SERAFILE 200/2 non-lubricated polyester filament and SERAFILE COM PHIL200/2 lubricated polyester filament).

A plurality of fibers includes 2 to hundreds or thousands or morefibers. The plurality of fibers can be in the form of bundles of strandsof fibers, referred to as tows, or in the form of relatively alignedstaple fibers referred to as sliver and roving. A single type fiber canbe used either alone or in combination with one or more different typesof fibers by co-mingling two or more types of fibers. Examples ofco-mingled fibers include polyester fibers with cotton fibers, glassfibers with carbon fibers, carbon fibers with aromatic polyimide(aramid) fibers, and aromatic polyimide fibers with glass fibers.

As used herein, the term “yarn” refers to an assembly including one ormore fibers, wherein the strand has a substantial length and arelatively small cross-section, and is suitable for use in theproduction of textiles by hand or by machine, including textiles madeusing weaving, knitting, crocheting, braiding, sewing, embroidery, orropemaking techniques. Thread is a type of yarn commonly used forsewing.

Yarns can be made using fibers comprising natural, man-made andsynthetic materials. Synthetic fibers are most commonly used to makespun yarns from staple fibers, and filament yarns. Spun yarn is made byarranging and twisting staple fibers together to make a cohesive strand.The process of forming a yarn from staple fibers typically includescarding and drawing the fibers to form sliver, drawing out and twistingthe sliver to form roving, and spinning the roving to form a strand.Multiple strands can be plied (twisted together) to make a thicker yarn.The twist direction of the staple fibers and of the plies can affect thefinal properties of the yarn. A filament yarn refer to a single long,substantially continuous filament, which is conventionally referred toas a “monofilament yarn,” or a plurality of individual filaments groupedtogether. A filament yarn can also refer to two or more long,substantially continuous filaments which are grouped together bygrouping the filaments together by twisting them or entangling them orboth. As with staple yarns, multiple strands can be plied together toform a thicker yarn.

Once formed, the yarn can undergo further treatment such as texturizing,thermal or mechanical treating, or coating with a material such as asynthetic polymer. The fibers, yarns, or textiles, or any combinationthereof, used in the disclosed articles can be sized. Sized fibers,yarns, and/or textiles are coated on at least part of their surface witha sizing composition selected to change the absorption or wearcharacteristics, or for compatibility with other materials. The sizingcomposition facilitates wet-out and wet-through of the coating or resinupon the surface and assists in attaining desired physical properties inthe final article. An exemplary sizing composition can comprise, forexample, epoxy polymers, urethane-modified epoxy polymers, polyesterpolymers, phenol polymers, polyamide polymers, polyurethane polymers,polycarbonate polymers, polyetherimide polymers, polyamideimidepolymers, polystylylpyridine polymers, polyimide polymers bismaleimidepolymers, polysulfone polymers, polyethersulfone polymers,epoxy-modified urethane polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone polymers, and mixtures thereof.

Two or more yarns can be combined, for example, to form composite yarnssuch as single- or double-covered yarns, and corespun yarns.Accordingly, yarns may have a variety of configurations that generallyconform to the descriptions provided herein.

The yarn can comprise at least one thermoplastic material (e.g., one ormore of the fibers can be made using a thermoplastic material). The yarncan be made of a thermoplastic material. The yarn can be coated with alayer of a material such as a thermoplastic material.

Various techniques exist for mechanically manipulating yarns to form atextile. Such techniques include, for example, interweaving,intertwining and twisting, and interlooping. Interweaving is theintersection of two yarns that cross and interweave at right angles toeach other. The yarns utilized in interweaving are conventionallyreferred to as “warp” and “weft.” A woven textile includes include awarp yarn and a weft yarn. The warp yarn extends in a first direction,and the weft strand extends in a second direction that is substantiallyperpendicular to the first direction. Intertwining and twistingencompasses various procedures, such as braiding and knotting, whereyarns intertwine with each other to form a textile. Interloopinginvolves the formation of a plurality of columns of intermeshed loops,with knitting being the most common method of interlooping. The textilemay be primarily formed from one or more yarns that aremechanically-manipulated, for example, through interweaving,intertwining and twisting, and/or interlooping processes, as mentionedabove.

The textile can be a nonwoven textile. Generally, a nonwoven textile orfabric is a sheet or web structure made from fibers and/or yarns thatare bonded together. The bond can be a chemical and/or mechanical bond,and can be formed using heat, solvent, adhesive or a combinationthereof. Exemplary nonwoven fabrics are flat or tufted porous sheetsthat are made directly from separate fibers, molten plastic and/orplastic film. They are not made by weaving or knitting and do notnecessarily require converting the fibers to yarn, although yarns can beused as a source of the fibers. Nonwoven textiles are typicallymanufactured by putting small fibers together in the form of a sheet orweb (similar to paper on a paper machine), and then binding them eithermechanically (as in the case of felt, by interlocking them with serratedor barbed needles, or hydro-entanglement such that the inter-fiberfriction results in a stronger fabric), with an adhesive, or thermally(by applying binder (in the form of powder, paste, or polymer melt) andmelting the binder onto the web by increasing temperature). A nonwoventextile can be made from staple fibers (e.g., from wetlaid, airlaid,carding/crosslapping processes), or extruded fibers (e.g., frommeltblown or spunbond processes, or a combination thereof), or acombination thereof. Bonding of the fibers in the nonwoven textile canbe achieved with thermal bonding (with or without calendering),hydro-entanglement, ultrasonic bonding, needlepunching (needlefelting),chemical bonding (e.g., using binders such as latex emulsions orsolution polymers or binder fibers or powders), meltblown bonding (e.g.,fiber is bonded as air attenuated fibers intertangle during simultaneousfiber and web formation).

Now having described various aspects of the present disclosure,additional discussion is provided regarding when the optical element isused in conjunction with a bladder. The bladder can be unfilled,partially inflated, or fully inflated when the structural design (e.g.,optical element) is disposed onto the bladder. The bladder is a bladdercapable of including a volume of a fluid. An unfilled bladder is afluid-fillable bladder and a filled bladder that has been at leastpartially inflated with a fluid at a pressure equal to or greater thanatmospheric pressure. When disposed onto or incorporated into an articleof footwear, apparel, or sports equipment, the bladder is generally, atthat point, a fluid-filled bladder. The fluid be a gas or a liquid. Thegas can include air, nitrogen gas (N₂), or other appropriate gas.

The bladder can have a gas transmission rate for nitrogen gas, forexample, where a bladder wall of a given thickness has a gastransmission rate for nitrogen that is at least about ten times lowerthan the gas transmission rate for nitrogen of a butyl rubber layer ofsubstantially the same thickness as the thickness of the bladderdescribed herein. The bladder can have a first bladder wall having afirst bladder wall thickness (e.g., about 0.1 to 40 mils). The bladdercan have a first bladder wall that can have a gas transmission rate(GTR) for nitrogen gas of less than about 15 cm³/m²·atm·day, less thanabout 10 m³/m²·atm·day, less than about 5 cm³/m²·atm·day, less thanabout 1 cm³/m²·atm·day (e.g., from about 0.001 cm³/m²·atm·day to about 1cm³/m²·atm·day, about 0.01 cm³/m²·atm·day to about 1 cm³/m²·atm·day orabout 0.1 cm³/m²·atm·day to about 1 cm³/m²·atm·day) for an average wallthickness of 20 mils. The bladder can have a first bladder wall having afirst bladder wall thickness, where the first bladder wall has a gastransmission rate of 15 cm³/m²·atm·day or less for nitrogen for anaverage wall thickness of 20 mils.

In an aspect, the bladder has a bladder wall having an interior-facingside and an exterior(or externally)-facing side, where the interior (orinternally)-facing side defines at least a portion of an interior regionof the bladder. The multi-layer optical film (or optical element) havinga first side and a second opposing side can be disposed on theexterior-facing side of the bladder, the interior-facing side of thebladder, or both. The exterior-facing side of the bladder, theinterior-facing side of the bladder, or both can include a plurality oftopographical structures (or profile features) extending from theexterior-facing side of the bladder wall, the interior-facing side ofthe bladder, or both, where the first side or the second side of themulti-layer optical film is disposed on the exterior-facing side of thebladder wall and covering the plurality of topographical structures, theinterior-facing side of the bladder wall and covering the plurality oftopographical structures, or both, and wherein the multi-layer opticalfilm imparts a achromatic structural color to the bladder wall.

In a particular aspect, the bladder can include a top wall operablysecured to the footwear upper, a bottom wall opposite the top wall, andone or more sidewalls extending between the top wall and the bottom wallof the inflated bladder. The top wall, the bottom wall, and the one ormore sidewalls collectively define an interior region of the inflatedbladder, and wherein the one or more sidewalls each comprise anexterior-facing side. The multi-layer optical film having a first sideand a second opposing side can be disposed on the exterior-facing sideof the bladder, the interior-facing side of the bladder, or both. Theexterior-facing side of the bladder, the interior-facing side of thebladder, or both can include a plurality of topographical structuresextending from the exterior-facing side of the bladder wall, theinterior-facing side of the bladder, or both, where the first side orthe second side of the multi-layer optical film is disposed on theexterior-facing side of the bladder wall and covering the plurality oftopographical structures, the interior-facing side of the bladder walland covering the plurality of topographical structures, or both, andwherein the multi-layer optical film imparts a achromatic structuralcolor to the bladder wall.

An accepted method for measuring the relative permeance, permeability,and diffusion of inflated bladders is ASTM D-1434-82-V. See, e.g., U.S.Pat. No. 6,127,026, which is incorporated by reference as if fully setforth herein. According to ASTM D-1434-82-V, permeance, permeability anddiffusion are measured by the following formulae:

Permeance

(quantity of gas)/[(area)×(time)×(pressure difference)]=permeance(GTR)/(pressure difference)=cm³/m²·atm·day (i.e., 24 hours)

Permeability

[(quantity of gas)×(film thickness)][(area)×(time)×(pressuredifference)]=permeability [(GTR)×(film thickness)]/(pressuredifference)=[(cm³)(mil)]/m²·atm·day (i.e., 24 hours)

Diffusion at One Atmosphere

(quantity of gas)/[(area)×(time)]=GTR=cm³/m²·day (i.e., 24 hours)

The bladder can include a bladder wall that includes a film including atleast one polymeric layer or at least two or more polymeric layers. Eachof the polymeric layers can be about 0.1 to 40 mils in thickness.

The polymeric layer can include a polymeric material such as athermoplastic material as described above and herein and can be thethermoplastic layer upon which the primer layer, the optical element canbe disposed, upon which the textured layer can be disposed, can be usedto form the textured layer, and the like. The thermoplastic material caninclude an elastomeric material, such as a thermoplastic elastomericmaterial. The thermoplastic materials can include thermoplasticpolyurethane (TPU), such as those described above and herein. Thethermoplastic materials can include polyester-based TPU, polyether-basedTPU, polycaprolactone-based TPU, polycarbonate-based TPU,polysiloxane-based TPU, or combinations thereof. Non-limiting examplesof thermoplastic material that can be used include: “PELLETHANE”2355-85ATP and 2355-95AE (Dow Chemical Company of Midland, Mich., USA),“ELASTOLLAN” (BASF Corporation, Wyandotte, Mich., USA) and “ESTANE”(Lubrizol, Brecksville, Ohio, USA), all of which are either ester orether based. Additional thermoplastic material can include thosedescribed in U.S. Pat. Nos. 5,713,141; 5,952,065; 6,082,025; 6,127,026;6,013,340; 6,203,868; and 6,321,465, which are incorporated herein byreference.

The polymeric layer can include a polymeric material including one ormore of the following polymers: ethylene-vinyl alcohol copolymers(EVOH), poly(vinyl chloride), polyvinylidene polymers and copolymers(e.g., polyvinylidene chloride), polyamides (e.g., amorphouspolyamides), acrylonitrile polymers (e.g., acrylonitrile-methyl acrylatecopolymers), polyurethane engineering plastics, polymethylpenteneresins, ethylene-carbon monoxide copolymers, liquid crystal polymers,polyethylene terephthalate, polyether imides, polyacrylic imides, andother polymeric materials known to have relatively low gas transmissionrates. Blends and alloys of these materials as well as with the TPUsdescribed herein and optionally including combinations of polyimides andcrystalline polymers, are also suitable. For instance, blends ofpolyimides and liquid crystal polymers, blends of polyamides andpolyethylene terephthalate, and blends of polyamides with styrenics aresuitable.

Specific examples of polymeric materials of the polymeric layer caninclude acrylonitrile copolymers such as “BAREX” resins, available fromIneos (Rolle, Switzerland); polyurethane engineering plastics such as“ISPLAST” ETPU available from Lubrizol (Brecksville, Ohio, USA);ethylene-vinyl alcohol copolymers marketed under the tradenames “EVAL”by Kuraray (Houston, Tex., USA), “SOARNOL” by Nippon Gohsei (Hull,England), and “SELAR OH” by DuPont (Wilmington, Del., USA);polyvinylidiene chloride available from S.C. Johnson (Racine, Wis., USA)under the tradename “SARAN”, and from Solvay (Brussels, Belgium) underthe tradename “IXAN”; liquid crystal polymers such as “VECTRA” fromCelanese (Irving, Tex., USA) and “XYDAR” from Solvay; “MDX6” nylon, andamorphous nylons such as “NOVAMID” X21 from Koninklijke DSM N.V(Heerlen, Netherlands), “SELAR PA” from DuPont; polyetherimides soldunder the tradename “ULTEM” by SABIC (Riyadh, Saudi Arabia); poly(vinylalcohol)s; and polymethylpentene resins available from Mitsui Chemicals(Tokyo, Japan) under the tradename “TPX”.

Each polymeric layer of the film can include a thermoplastic materialwhich can include a combination of thermoplastic polymers. In additionto one or more thermoplastic polymers, the thermoplastic material canoptionally include a colorant, a filler, a processing aid, a freeradical scavenger, an ultraviolet light absorber, and the like. Eachpolymeric layer of the film can be made of a different of thermoplasticmaterial including a different type of thermoplastic polymer.

The bladder can be made by applying heat, pressure and/or vacuum to afilm. In this regard, the primer layer, the optical element, thetextured layer, and the like can be disposed, formed from, or the likeprior to, during, and/or after these steps. The bladder (e.g., one ormore polymeric layers) can be formed using one or more polymericmaterials, and forming the bladder using one or more processingtechniques including, for example, extrusion, blow molding, injectionmolding, vacuum molding, rotary molding, transfer molding, pressureforming, heat sealing, casting, low-pressure casting, spin casting,reaction injection molding, radio frequency (RF) welding, and the like.The bladder can be made by co-extrusion followed by heat sealing orwelding to give an inflatable bladder, which can optionally include oneor more valves (e.g., one way valves) that allows the bladder to befilled with the fluid (e.g., gas).

Now having described the optical element, the optional textured surface,and methods of making the article are now described. In an aspect, themethod includes forming the reflective layer (base reflective layer) ofthe optical element. In an aspect, the method includes forming thereflective layer on a surface of an article such as a textile, film,fiber, or monofilament yarn, where the surface can optionally be thetextured surface. The reflective layer can be formed using one or moretechniques described herein.

The method provides for the reflective layer being formed on the surface(e.g., three dimensional flat planar surfaces or substantially threedimensional flat planar surfaces or textured surface). Subsequently, theconstituent layers can be disposed on the reflective layer.Alternatively, the textured surface can be formed in/on the reflectivelayer, and then the constituent layers are disposed on the reflectivelayer. As described herein, the optical element can be formed in alayer-by-layer manner, where each constituent layer has a differentindex of refraction. As each layer is formed the undulations and flatregions are altered. The combination of the optional textured surface(e.g., dimensions, shape, and/or spacing of the profile elements) andthe layers of the optical element (e.g., number of layers, thickness oflayers, material of the layers) and the resultant undulations and planarareas impart the achromatic structural color when exposed to visiblelight. The method includes optionally forming a protective layer overthe optical element to protect the optical element.

Another embodiment of the present disclosure includes providingreflective layer and the textured surface on the substrate, where thereflective layer (base reflective layer) can be disposed on the texturedsurface. Each constituent layer of the optical element can be formed inturn, where each layer can be formed then after an appropriate amount oftime, additional processing, cooling, or the like, the next layer of theoptical element can be formed. Optionally, non-base reflective layer(s)can be formed between constituent layers. Optionally, the opticalelement does not include a reflective layer. Optionally, the top layer,by itself or in combinations with one or more reflective layers, can beformed on the last constituent layer (one on the side opposite the basereflective layer).

It should be emphasized that the above-described aspects of the presentdisclosure are merely possible examples of implementations, and are setforth only for a clear understanding of the principles of thedisclosure. Many variations and modifications may be made to theabove-described aspects of the disclosure without departingsubstantially from the spirit and principles of the disclosure. All suchmodifications and variations are intended to be included herein withinthe scope of this disclosure.

The word “disposing” can be replaced with “operably disposing” in eachof the claims.

Measurements for visible light transmittance and visible lightreflectance were performed using a Shimadzu UV-2600 Spectrophotometer(Shimadzu Corporation, Japan). The spectrometer was calibrated using astandard prior to the measurements. The incident angle for allmeasurements was zero, unless the incident angle is intentionallyaltered. The wavelength resolution can be measured at 0.1 nm.

The visible light transmittance was the measurement of visible light (orlight energy) that was transmitted through a sample material whenvisible light within the spectral range of 400 nanometers to 800nanometers was directed through the material. The results of alltransmittance over the range of 400 nanometers to 800 nanometers wascollected and recorded. For each sample, a minimum value for the visiblelight transmittance was determined for this range.

The visible light reflectance was a measurement of the visible light (orlight energy) that was reflected by a sample material when visible lightwithin the spectral range of 400 nanometers to 800 nanometers wasdirected through the material. The results of all reflectance over therange of 400 nanometers to 800 nanometers was collected and recorded.For each sample, a minimum value for the visible light reflectance wasdetermined for this range.

It should be noted that ratios, concentrations, amounts, and othernumerical data may be expressed herein in a range format. It is to beunderstood that such a range format is used for convenience and brevity,and thus, should be interpreted in a flexible manner to include not onlythe numerical values explicitly recited as the limits of the range, butalso to include all the individual numerical values or sub-rangesencompassed within that range as if each numerical value and sub-rangeis explicitly recited. To illustrate, a concentration range of “about0.1 percent to about 5 percent” should be interpreted to include notonly the explicitly recited concentration of about 0.1 weight percent toabout 5 weight percent but also include individual concentrations (e.g.,1 percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges(e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4percent) within the indicated range. The term “about” can includetraditional rounding according to significant figures of the numericalvalue. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ toabout ‘y’”.

The term “providing”, such as for “providing an article” and the like,when recited in the claims, is not intended to require any particulardelivery or receipt of the provided item. Rather, the term “providing”is merely used to recite items that will be referred to in subsequentelements of the claim(s), for purposes of clarity and ease ofreadability.

Many variations and modifications may be made to the above-describedaspects. All such modifications and variations are intended to beincluded herein within the scope of this disclosure and protected by thefollowing claims.

We claim:
 1. An article comprising: an optical element on a surface ofthe article, wherein the optical element imparts a structural color tothe article, wherein the structural color is an achromatic color.
 2. Thearticle of claim 1, wherein the achromatic color is black.
 3. Thearticle of claim 2, wherein the optical element reflects all wavelengthswithin the range of about 380 to 740 nanometers to substantially thesame degree.
 4. The article of claim 2, wherein the percent reflectanceof the optical element is about 2 percent or less within the range ofabout 380 to 740 nanometers.
 5. The article of claim 2, wherein thepercent absorbance of the optical element is about 98 percent or morewithin the range of about 380 to 740 nanometers.
 6. The article of claim1, wherein the achromatic color is white.
 7. The article of claim 6,wherein the optical element absorbs all wavelengths within the range ofabout 380 to 740 nanometers to substantially the same degree.
 8. Thearticle of claim 6, wherein the percent absorbance of the opticalelement is about 2 percent or less within the range of about 380 to 740nanometers.
 9. The article of claim 6, wherein the percent reflectanceof the optical element is about 98 percent or more within the range ofabout 380 to 740 nanometers.
 10. The article of claim 4, wherein theachromatic color is neutral gray.
 11. The article of claim 10, whereinthe percent absorbance of the optical element is about 2 to 98 withinthe range of about 380 to 740 nanometers.
 12. The article of claim 10,wherein the percent reflectance of the optical element is about 2 to 98within the range of about 380 to 740 nanometers.
 13. The article ofclaim 1, wherein the achromatic structural color has no hue or chroma.14. The article of claim 1, wherein the achromatic structural color isindependent of an angle of observation angle.
 15. The article of claim1, wherein the optical element absorbs all wavelengths within the rangeof about 380 to 740 nanometers to substantially the same degree orwherein the optical element reflects all wavelengths within the range ofabout 380 to 740 nanometers to substantially the same degree, or bothand wherein an observer having 20/20 visual acuity and normal colorvision from a distance of about 1 meter from the article considers thestructural color achromatic.
 16. The article of claim 1, wherein theoptical element is an inorganic optical element, an organic opticalelement, or a mixed inorganic/organic optical element.
 17. The articleof claim 1, wherein the optical element includes at least one layerhaving an undulating topography, wherein the achromatic structural coloris unaffected by the undulating topography of the at least one layer ofthe optical element.
 18. The article of claim 1, wherein the article isan article of footwear, a component of footwear, an article of apparel,a component of apparel, an article of sporting equipment, or a componentof sporting equipment.
 19. The article of any claim 1, wherein thearticle is a non-woven synthetic leather.
 20. The article of claim 1,wherein the optical element imparts a shifting achromatic structuralcolor as the angle of observation or illumination changes by 10 degreesor more.